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| United States Patent |
6,114,546
|
|
Yasuda
, et al.
|
September 5, 2000
|
Aminomethylene derivatives and ultraviolet absorbent comprising thereof
Abstract
The present invention provides an aminomethylene derivative represented by
general formula (I):
##STR1##
wherein A is a cyclic oxo group selected from the group consisting of
following general formulae (a), (b), (c), (d) and (e):
##STR2##
wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 each independently
represent H, an alkyl group or the like; R.sup.6, R.sup.7 and R.sup.8 each
independently represent an alkyl group or the like; R.sup.1 and R.sup.2 or
R.sup.7 and R.sup.8 may combine with each other to form a tetramethylene
group or the like; R represents an alkyl group optionally containing OH or
O; and n is an integer of 0 to 4, a process for the same, and the use
thereof. The derivatives have an excellent ultraviolet absorption ability
and a high optical stability.
| Inventors:
|
Yasuda; Heinosuke (Koube, JP);
Hukuoka; Naohiko (Koube, JP)
|
| Assignee:
|
Chemipro Kasei Kaisha, Limited (Koube, JP)
|
| Appl. No.:
|
269401 |
| Filed:
|
March 26, 1999 |
| PCT Filed:
|
October 3, 1997
|
| PCT NO:
|
PCT/JP97/03536
|
| 371 Date:
|
March 26, 1999
|
| 102(e) Date:
|
March 26, 1999
|
| PCT PUB.NO.:
|
WO98/14423 |
| PCT PUB. Date:
|
April 6, 1998 |
Foreign Application Priority Data
| Oct 04, 1996[JP] | 8-283345 |
| Oct 18, 1996[JP] | 8-297277 |
| Oct 29, 1996[JP] | 8-303697 |
| May 27, 1997[JP] | 9-152909 |
| Jun 19, 1997[JP] | 9-179052 |
| Current U.S. Class: |
549/285; 544/302; 549/274; 568/376 |
| Intern'l Class: |
C07D 311/56 |
| Field of Search: |
549/285
|
References Cited
| Foreign Patent Documents |
| 3-38554 | Feb., 1991 | JP.
| |
| 7-89901 | Apr., 1995 | JP.
| |
Other References
Uray, G. et al., ".beta., .beta.-Diacyl-enamine Und-enole," Journal of
Molecular Structure, 54, 1979, pp. 77-88.
|
Primary Examiner: Raymond; Richard L.
Assistant Examiner: Balasubramanian; Venkataraman
Attorney, Agent or Firm: Oliff & Berridge, PLC
Parent Case Text
This application is a 371 of PCT/JP97/03536, filed Oct. 3, 1997.
Claims
What is claimed is:
1. An aminomethylene derivative represented by general formula (I):
##STR19##
wherein A is a cyclic oxo group of following general formula (d):
##STR20##
wherein R.sup.6 is a group selected from the group consisting of linear or
branched, saturated or unsaturated alkyl groups, cycloalkyl groups,
aralkyl groups, aryl groups, alkoxy groups, alkoxycarbonyl groups, acyl
groups, dialkylamino groups and halogens, and R is a group selected from
the group consisting of linear or branched, saturated or unsaturated alkyl
groups, aralkyl groups, aryl groups, cycloalkyl groups and
alkoxycarbonylalkylene groups, and n is an integer of 0 to 4 wherein when
n is 2 or more, each of plural R.sup.6 s can be different groups within
the above-described groups.
2. A method for producing an aminomethylene derivative represented by
general formula (I):
##STR21##
wherein A is following general formula (d):
##STR22##
wherein R.sup.6 is a group selected from the group consisting of linear or
branched, saturated or unsaturated alkyl groups, cycloalkyl groups,
aralkyl groups, aryl groups, alkoxy groups, alkoxycarbonyl groups, acyl
groups, dialkylamino groups and halogens, and R is a group selected from
the group consisting of linear or branched, saturated or unsaturated alkyl
groups, aralkyl groups, aryl groups, cycloalkyl groups and
alkoxycarbonylalkylene groups, and n is an integer of 0 to 4 wherein when
n is 2 or more, each of plural R.sup.6 s can be different groups within
the above-described groups,
wherein a cyclic oxo compound represented by general formula (II):
A' (II)
wherein A' is a compound of following general formula (d):
##STR23##
wherein R.sup.6 is a group selected from the group consisting of linear or
branched, saturated or unsaturated alkyl groups, cycloalkyl groups,
aralkyl groups, aryl groups, alkoxy groups, alkoxycarbonyl groups, acyl
groups, dialkylamino groups and halogens, and n is an integer of 0 to 4
wherein when n is 2 or more, each of plural R.sup.6 s can be different
groups within the above-described groups,
is allowed to react with an N-formylaminobenzoate derivative represented by
general formula (III):
##STR24##
wherein R is a group selected from the group consisting of linear or
branched, saturated or unsaturated alkyl groups, cycloalkyl groups,
aralkyl groups, aryl groups and alkoxycarbonylalkylene groups,
in an organic solvent and in the presence of a halide.
3. A method according to claim 2, wherein said halide is a chloride.
Description
TECHNICAL FIELD
The present invention relates to aminomethylene derivatives having
excellent ultraviolet absorptivity and high light stability, and
ultraviolet absorbent, cosmetic materials and weatherproofing polymer
composition comprising thereof, and methods for producing above described
aminomethylene derivatives.
PRIOR ART
It has been known that organic substances, especially polymer compounds,
are subjected to yellowing, discoloration, cracking or embrittlement by
the action of ultraviolet rays. Meanwhile, ultraviolet rays that reach to
the ground surface consist mostly of UV-B (280 to 320 nm) and UV-A (320 to
400 nm). Among them, ultraviolet rays of the UV-A range, when more than a
certain amount of them is applied to the skin, cause rash or blisters and
are also considered to causes lowering of elasticity or browning of the
skin. In order to prevent such changes of the skin caused by ultraviolet
rays of the UV-A range, so called sunscreen cosmetics which contain
ultraviolet absorbent are known. As known ultraviolet absorbents that have
been used there are benzophenone derivatives including
4-phenylbenzophenone and 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid,
dibenzoylmethane derivatives including
4-tert-butyl-4'-methoxydibenzoylmethane, and benzotriazole derivatives
including 2-(2-hydroxy-5-methoxyphenyl)benzotriazole.
Above described conventional synthetic compounds which are used as
ultraviolet absorbent for UV-A in organic substances, especially in
polymer compounds, have defect that they react with metal ions and cause
coloring. Further, since ultraviolet absorbents themselves are colored in
general, the amount of use is restricted. On the other hand,
conventionally known synthetic compounds used as UV-A absorbents which are
usually added to cosmetic materials and others, have limits on the amount
can be used because of their irritativeness to the skin, and therefore,
they cannot be used at the sufficient amount required for protecting the
skin from sunburn and can provide only smaller UV-A protection effect.
Therefore, development of a synthetic compound that absorbs ultraviolet
rays of the UV-A range and shows much high absorption, in other words has
higher molecular absorptivity, has been expected.
OBJECT OF THE INVENTION
The primary object of the present invention is to provide a novel compound
showing much high absorption, in other words has higher molecular
absorptivity, and a method for producing the same.
The second object of the present invention is to provide a novel
ultraviolet absorbent through utilizing above described ultraviolet
absorptivity, a cosmetic material and a weatherproofing organic polymer
composition including thereof.
DISCLOSURE OF THE INVENTION
The first aspect of the present invention relates to an aminomethylene
derivative represented by general formula (I):
##STR3##
in which A is a cyclic oxo group selected from the group consisting of
following general formulae (a), (b), (c), (d) and (e),
##STR4##
wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 each independently
are groups selected from the group consisting of a hydrogen atom, linear
or branched, saturated or unsaturated alkyl groups, cycloalkyl groups,
aralkyl groups and aryl groups, R.sup.6 is a group selected from the group
consisting of linear or branched, saturated or unsaturated alkyl groups,
cycloalkyl groups, aralkyl groups, aryl groups, a hydroxyl group, alkoxy
groups, alkoxycarbonyl groups, acyl groups, an amino group, acylamino
groups, alkylamino groups, dialkylamino groups, arylamino groups and
halogens, R.sup.7 and R.sup.8 each independently are groups selected from
the group consisting of linear or branched, saturated or unsaturated alkyl
groups, cycloalkyl groups, aralkyl groups and aryl groups, further R.sup.1
and R.sup.2 or R.sup.7 and R.sup.8 can, together, form a tetramethylene
group, pentamethylene group or hexamethylene group, and R is a group
selected from the group consisting of linear or branched, saturated or
unsaturated alkyl groups, aralkyl groups, aryl groups, cycloalkyl groups,
alkyl groups containing hydroxyl group, alkoxycarbonylalkylene groups and
alkyl groups containing oxygen atom, and n is an integer of 0 to 4 wherein
when n is 2 or more, each of plural R.sup.6 s can be different groups
within above described groups.
The second aspect of the present invention relates to an ultraviolet
absorbent containing said aminomethylene derivative.
The third aspect of the present invention relates to a cosmetic material
containing said aminomethylene derivative.
The fourth aspect of the present invention relates to a weatherproofing
organic polymer composition containing said aminomethylene derivative.
The fifth aspect of the present invention relates to a method for producing
an aminomethylene derivative represented by following general formula (I):
##STR5##
wherein A is a cyclic oxo group selected from the group consisting of
following general formulae (a), (b), (c), (d) and (e):
##STR6##
wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 each independently
are groups selected from the group consisting of a hydrogen atom, linear
or branched, saturated or unsaturated alkyl groups, cycloalkyl groups,
aralkyl groups and aryl groups, R.sup.6 is a group selected from the group
consisting of linear or branched, saturated or unsaturated alkyl groups,
cycloalkyl groups, aralkyl groups, aryl groups, a hydroxyl group, alkoxy
groups, alkoxycarbonyl groups, acyl groups, an amino group, acylamino
groups, alkylamino groups, dialkylamino groups, arylamino groups and
halogens, R.sup.7 and R.sup.8 each independently are groups selected from
the group consisting of linear or branched, saturated or unsaturated alkyl
groups, cycloalkyl groups, aralkyl groups and aryl groups, further R.sup.1
and R.sup.2 or R.sup.7 and R.sup.8 can, together, form a tetramethylene
group, pentamethylene group or hexamethylene group, and R is a group
selected from the group consisting of linear or branched, saturated or
unsaturated alkyl groups, aralkyl groups, aryl groups, cycloalkyl groups,
alkyl groups containing hydroxyl group, alkoxycarbonylalkylene groups and
alkyl groups containing oxygen atom, and n is an integer of 0 to 4 wherein
when n is 2 or more, each of plural R.sup.6 s can be different groups
within above described groups, characterised in that a cyclic oxo compound
represented by the general formula (II):
A' (II)
wherein A' is a compound selected from the group consisting of following
general formulae (a'), (b'), (c'), (d') and (e'):
##STR7##
wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 each independently
are groups selected from the group consisting of an hydrogen atom, linear
or branched, saturated or unsaturated alkyl groups, cycloalkyl groups,
aralkyl groups and aryl groups, R.sup.6 is a group selected from the group
consisting of linear or branched, saturated or unsaturated alkyl groups,
cycloalkyl groups, aralkyl groups, aryl groups, a hydroxyl group, alkoxy
groups, alkoxycarbonyl groups, acyl groups, an amino group, acylamino
groups, alkylamino groups, dialkylamino groups, arylamino groups and
halogens, R.sup.7 and R.sup.8 each independently are groups selected from
the group consisting of linear or branched, saturated or unsaturated alkyl
groups, cycloalkyl groups, aralkyl groups and aryl groups, further R.sup.1
and R.sup.2 or R.sup.7 and R.sup.8 can, together form a tetramethylene
group, pentamethylene group or hexamethylene group, and n is an integer of
0 to 4 wherein when n is 2 or more, each of plural R.sup.6 s can be
different groups within above described groups, is allowed to react with
an N-formylamino benzoate derivative represented by general formula (III):
##STR8##
wherein R is a group selected from the group consisting of linear or
branched, saturated or unsaturated alkyl groups, cycloalkyl groups,
aralkyl groups, aryl groups, alkyl groups containing hydroxyl group,
alkoxycarbonylalkylene groups and alkyl groups containing oxygen atom, in
organic solvent and in the presence of an acid catalyst.
Regarding to R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5, examples of
linear or branched, saturated or unsaturated alkyl groups include methyl,
ethyl, propyl, isopropyl, butyl, isobutyl, or allyl groups but those
having 1 to 8 carbon atoms are preferable. Examples of above described
cycloalkyl groups include cyclopentyl and cyclohexyl. Examples of above
described aralkyl groups include those of which one hydrogen of said alkyl
groups is substituted by a phenyl group, such as phenylethyl and
phenylpropyl groups. Examples of above described aryl groups include a
phenyl group and phenyl groups substituted by methyl, methoxy, ethoxy,
methoxycarbonyl, ethoxycarbonyl, halogen, acetyl, cyano group or the like.
Regarding to R.sup.6, examples of above described linear or branched,
saturated or unsaturated alkyl groups include methyl, ethyl, n-propyl,
isopropyl, n-butyl, isobutyl, t-butyl, allyl, but those having 1 to 8
carbon atoms are preferable. Examples of above described cycloalkyl groups
include cyclopentyl and cyclohexyl groups. Examples of above described
aralkyl groups include those of which one hydrogen of said alkyl groups is
substituted by a phenyl group, such as benzyl, phenylethyl and
phenylpropyl groups. Examples of above described aryl groups include a
phenyl group and phenyl groups substituted by alkyl groups such as methyl
and ethyl, alkoxyl groups such as methoxy and ethoxy, alkoxycarbonyl
groups such as methoxycarbonyl and ethoxycarbonyl, or other substituent
such as a halogen, acetyl and cyano.
Examples of above described alkoxy groups include methoxy group, ethoxy
group, n-propoxy group, isopropoxy group and n-butoxy group. Examples of
above described alkoxycarbonyl groups include methoxycarbonyl group and
ethoxycarbonyl group. Examples of above described acyl groups include
acetyl group, n-propionyl group and isopropionyl group. Examples of above
described acylamino groups include acetylamino group and n-propionylamino
group. Examples of above described alkylamino groups include amino groups
having above described alkyl groups, such as methylamino group and
ethylamino group. Examples of above described dialkylamino groups include
dimethylamino group and diethylamino group. Examples of above described
arylamino groups include amino groups having above described aryl groups,
such as phenylamino group, tolylamino group, anisylamino group.
Regarding R.sup.7 and R.sup.8, examples of above described linear or
branched, saturated or unsaturated alkyl groups include methyl, ethyl,
n-propyl, isopropyl, n-butyl, isobutyl and allyl groups, but those having
1 to 8 carbon atoms are preferable. Examples of above described cycloalkyl
groups include cyclopentyl and cyclohexyl groups. Examples of above
described aralkyl groups include those of which one hydrogen of said alkyl
groups is substituted by a phenyl group, such as phenylethyl and
phenylpropyl groups. Examples of above described aryl groups include a
phenyl group and phenyl groups substituted by methyl, methoxy, ethoxy,
methoxycarbonyl, ethoxycarbonyl, halogen, acetyl, cyano or the like.
Further R.sup.1 and R.sup.2 or R.sup.7 and R.sup.8 can, together form a
tetramethylene group, pentamethylene group or hexamethylene group.
Regarding R, examples of above described linear or branched, saturated or
unsaturated alkyl groups include methyl group, ethyl group, n-propyl
group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group,
tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group,
2-ethylhexyl group, n-octyl group, n-nonyl group, isononyl group, n-decyl
group, n-undecyl group, n-dodecyl group, n-tridecyl group, iso-tridecyl
group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group,
n-heptadecyl group, n-octadecyl group, n-eicosyl group, allyl group and
propene group, but those having carbon atoms of 1 to 20 are preferable.
Longer alkyl groups also can be used, in that case, synthesis is performed
using oxo process or the Ziegler process. Examples of above described
aralkyl groups, cycloalkyl groups and aryl groups can be the same with the
examples described regarding to R.sup.1 and R.sup.2. Examples of above
described alkyl group having hydroxyl group includes methylol group and
ethylol group. Examples of above described alkoxycarbonylalkylene groups
include methoxycarbonylmethyl group, ethoxycarbonylmethyl group and
2-ethylhexyloxylcarbonylmethyl group. Examples of above described alkyl
groups having oxygen atom include methoxyethyl group, ethoxyethyl group
and methoxyethyloxy group.
Above described reaction is generally performed at a temperature range of
10 to 60.degree. C., preferably 30 to 50.degree. C., and examples of
organic solvent used for the reaction can be any solvent that dissolves
compounds represented by the general formula (I) and (II), respectively
and include aromatic hydrocarbons and halogenated alkyls, such as toluene,
xylene, dichloroethylene and chloroform.
Examples of above described acid catalyst include phosphorus pentachloride,
phosphorus trichloride, phosphorus oxychloride, thionyl chloride and
sulfuryl chloride.
Organic materials stabilized by the compound represented by the general
formula (I), for example cosmetic materials and polymer materials, can
further include conventionally used additives such as an antioxidant,
light stabilizing agent, metal deactivator and peroxide scavenger.
Said organic materials may be natural or synthetic polymers, for example
cellulose, CMC, natural rubbers, synthetic rubbers such as SBR, NBR or the
like, polyolefins such as polyethylene, polypropylene or the like,
synthetic resins such as polyester, polyamide, polyurethane, polyvinyl
chloride or the like, and so on.
Of the aminomethylene derivatives represented by the general formula (I)
used in the present invention, concrete examples of
aminomethylenecyclohexane derivatives in which A in the formula (I) is
(a), represented by the formula (Ia):
##STR9##
wherein R.sup.1, R.sup.2 and R are as defined above, include following
compounds:
2-(4-ethoxycarbonylphenylamino)-methylene-1,3-cyclohexadione;
2-(4-isopropoxycarbonylphenylamino)-methylene-1,3-cyclohexadione;
2-(4-isobutoxycarbonylphenylamino)-methylene-1,3-cyclohexadione;
2-(4-sec-butoxycarbonylphenylamino)-methylene-1,3-cyclohexadione;
2-(4-tert-butoxycarbonylphenylamino)-methylene-1,3-cyclohexadione;
2-(4-n-pentyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;
2-(4-n-hexyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;
2-(4-n-heptyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;
2-(4-n-nonyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;
2-(4-n-decyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;
2-(4-n-undecyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;
2-(4-n-dodecyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;
2-(4-n-tridecyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;
2-(4-n-tetradecyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;
2-(4-n-pentadecyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;
2-(4-n-hexadecyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;
2-(4-n-heptadecyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione;
5,5-dimethyl-2-(4-ethoxycarbonylphenylamino)-methylene-1,3-cyclohexadione;
5,5-dimethyl-2-(4-isopropoxycarbonylphenylamino)-methylene-1,3-cyclohexadio
ne;
5,5-dimethyl-2-(4-isobutoxycarbonylphenylamino)-methylene-1,3-cyclohexadion
e;
5,5-dimethyl-2-(4-sec-butoxycarbonylphenylamino)-methylene-1,3-cyclohexadio
ne;
5,5-dimethyl-2-(4-tert-butoxycarbonylphenylamino)-methylene-1,3-cyclohexadi
one;
5,5-dimethyl-2-(4-n-pentyloxycarbonylphenylamino)-methylene-1,3-cyclohexadi
one;
5,5-dimethyl-2-(4-n-hexyloxycarbonylphenylamino)-methylene-1,3-cyclohexadio
ne;
5,5-dimethyl-2-(4-n-heptyloxycarbonylphenylamino)-methylene-1,3-cyclohexadi
one;
5,5-dimethyl-2-(4-n-nonyloxycarbonylphenylamino)-methylene-1,3-cyclohexadio
ne;
5,5-dimethyl-2-(4-n-decyloxycarbonylphenylamino)-methylene-1,3-cyclohexadio
ne;
5,5-dimethyl-2-(4-n-undecyloxycarbonylphenylamino)-methylene-1,3-cyclohexad
ione;
5,5-dimethyl-2-(4-n-dodecyloxycarbonylphenylamino)-methylene-1,3-cyclohexad
ione;
5,5-dimethyl-2-(4-n-tridecyloxycarbonylphenylamino)-methylene-1,3-cyclohexa
dione;
5,5-dimethyl-2-(4-n-tetradecyloxycarbonylphenylamino)-methylene-1,3-cyclohe
xadione;
5,5-dimethyl-2-(4-n-pentadecyloxycarbonylphenylamino)-methylene-1,3-cyclohe
xadione;
5,5-dimethyl-2-(4-n-hexadecyloxycarbonylphenylamino)-methylene-1,3-cyclohex
adione;
5,5-dimethyl-2-(4-n-heptadecyloxycarbonylphenylamino)-methylene-1,3-cyclohe
xadione;
5,5-diethyl-2-(4-methoxycarbonylphenylamino)-methylene-1,3-cyclohexadione;
5,5-diethyl-2-(4-ethoxycarbonylphenylamino)-methylene-1,3-cyclohexadione;
5,5-diethyl-2-(4-n-propoxycarbonylphenylamino)-methylene-1,3-cyclohexadione
;
5,5-diethyl-2-(4-isopropoxycarbonylphenylamino)-methylene-1,3-cyclohexadion
e;
5,5-diethyl-2-(4-n-butoxycarbonylphenylamino)-methylene-1,3-cyclohexadione;
5,5-diethyl-2-(4-n-pentyloxycarbonylphenylamino)-methylene-1,3-cyclohexadio
ne;
5,5-diethyl-2-(4-n-hexyloxycarbonylphenylamino)-methylene-1,3-cyclohexadion
e;
5,5-diethyl-2-(4-n-heptyloxycarbonylphenylamino)-methylene-1,3-cyclohexadio
ne;
5,5-diethyl-2-[4-(2-ethylhexyloxycarbonylphenylamino)]-methylene-1,3-cycloh
exadione;
5,5-diethyl-2-(4-n-octadecyloxycarbonylphenylamino)-methylene-1,3-cyclohexa
dione;
5,5-dimethyl-2-(4-methoxyethylcarbonylphenylamino)-methylene-1,3-cyclohexad
ione;
5,5-dimethyl-2-(4-ethoxyethylcarbonylphenylamino)-methylene-1,3-cyclohexadi
one;
5,5-dimethyl-2-(4-methoxycarbomethyloxycarbonylphenylamino)-methylene-1,3-c
yclohexadione;
5,5-dimethyl-2-(4-ethoxycarbomethyloxycarbonylphenylamino)-methylene-1,3-cy
clohexadione;
5,5-diethyl-2-(4-methoxyethylcarbonylphenylamino)-methylene-1,3-cyclohexadi
one;
5,5-diethyl-2-(4-ethoxyethylcarbonylphenylamino)-methylene-1,3-cyclohexadio
ne;
5,5-diethyl-2-(4-methoxycarbomethyloxycarbonylphenylamino)-methylene-1,3-cy
clohexadione;
5,5-diethyl-2-(4-ethoxycarbomethyloxycarbonylphenylamino)-methylene-1,3-cyc
lohexadione, and so on.
Of the aminomethylene derivatives represented by the general formula (I)
used in the present invention, concrete examples of aminomethylene pyrone
derivatives in which A in formula (I) is (b), represented by the formula
(Ib):
##STR10##
wherein R.sup.3 and R are as defined above, include following compounds:
6-methyl-3-(4-ethoxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dion
e;
6-methyl-3-(4-isopropoxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-d
ione;
6-methyl-3-(4-isobutoxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-di
one;
6-methyl-3-(4-sec-butoxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-d
ione;
6-methyl-3-(4-tert-butoxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-
dione;
6-methyl-3-(4-n-pentyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-
dione;
6-methyl-3-(4-n-hexyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-d
ione;
6-methyl-3-(4-n-heptyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-
dione;
6-methyl-3-(4-n-nonyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-d
ione;
6-methyl-3-(4-n-decyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-d
ione;
6-methyl-3-(4-n-undecyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4
-dione;
6-methyl-3-(4-n-dodecyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4
-dione;
6-methyl-3-(4-n-tridecyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,
4-dione;
6-methyl-3-(4-n-tetradecyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-
2,4-dione;
6-methyl-3-(4-n-pentadecyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-
2,4-dione;
6-methyl-3-(4-n-hexadecyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2
,4-dione;
6-methyl-3-(4-n-heptadecyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-
2,4-dione;
6-ethyl-3-(4-methoxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione
;
6-ethyl-3-(4-ethoxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dione;
6-ethyl-3-(4-n-propoxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dio
ne;
6-ethyl-3-(4-isopropoxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-di
one;
6-ethyl-3-(4-n-butoxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-dion
e;
6-ethyl-3-(4-n-pentyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-d
ione;
6-ethyl-3-(4-n-hexyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-di
one;
6-ethyl-3-(4-n-heptyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-d
ione;
6-ethyl-3-[4-(2-ethylhexyloxycarbonylphenyl)aminomethylene]-2H,3H,4H-pyrane
-2,4-dione;
6-ethyl-3-(4-n-octadecyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,
4-dione;
6-methyl-3-(4-methoxylethylcarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,
4-dione;
6-methyl-3-(4-ethoxyethylcarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-
dione;
5-methyl-3-(4-methoxycarbonylmethyloxycarbonylphenylaminomethylene)-2H,3H,4
H-pyrane-2,4-dione;
6-methyl-3-(4-ethoxycarbonylmethyloxycarbonylphenylaminomethylene)-2H,3H,4H
-pyrane-2,4-dione;
6-ethyl-3-(4-methoxyethylcarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-
dione;
6-ethyl-3-(4-ethoxyethylcarbonylphenylaminomethylene)-2H,3H,4H-pyrane-2,4-d
ione;
6-ethyl-3-(4-methoxycarbonylmethyloxycarbonylphenylaminomethylene)-2H,3H,4H
-pyrane-2,4-dione;
6-ethyl-3-(4-ethoxycarbonylmethyloxycarbonylphenylaminomethylene)-2H,3H,4H-
pyrane-2,4-dione, and so on.
Of the aminomethylene derivatives represented by the general formula (I)
used in the present invention, concrete examples of aminomethylene
barbituric acid derivatives in which A in the formula (I) is (c),
represented by the formula (Ic):
##STR11##
wherein R.sup.4, R.sup.5 and R are as defined above, include following
compounds:
1,3-dimethyl-5-(4-ethoxycarbonylphenylamino)-methylene-barbituric acid;
1,3-dimethyl-5-(4-isopropoxycarbonylphenylamino)-methylene-barbituric acid;
1,3-dimethyl-5-(4-isobutoxycarbonylphenylamino)-methylene-barbituric acid;
1,3-dimethyl-5-(4-sec-butoxycarbonylphenylamino)-methylene-barbituric acid;
1,3-dimethyl-5-(4-tert-butoxycarbonylphenylamino)-methylene-barbituric
acid;
1,3-dimethyl-5-(4-n-pentyloxycarbonylphenylamino)-methylene-barbituric
acid;
1,3-dimethyl-5-(4-n-hexyloxycarbonylphenylamino)-methylene-barbituric acid;
1,3-dimethyl-5-(4-n-heptyloxycarbonylphenylamino)-methylene-barbituric
acid;
1,3-dimethyl-5-(4-n-nonyloxycarbonylphenylamino)-methylene-barbituric acid;
1,3-dimethyl-5-(4-n-decyloxycarbonylphenylamino)-methylene-barbituric acid;
1,3-dimethyl-5-(4-n-undecyloxycarbonylphenylamino)-methylene-barbituric
acid;
1,3-dimethyl-5-(4-n-dodecyloxycarbonylphenylamino)-methylene-barbituric
acid;
1,3-dimethyl-5-(4-n-tridodecyloxycarbonylphenylamino)-methylene-barbituric
acid;
1,3-dimethyl-5-(4-n-tetradodecyloxycarbonylphenylamino)methylene-barbituric
acid;
1,3-dimethyl-5-(4-n-pentadecyloxycarbonylphenylamino)-methylene-barbituric
acid;
1,3-dimethyl-5-(4-n-hexadecyloxycarbonylphenylamino)-methylene-barbituric
acid;
1,3-dimethyl-5-(4-n-heptadecyloxycarbonylphenylamino)-methylene-barbituric
acid;
1,3-diethyl-5-(4-methoxycarbonylphenylamino)-methylene-barbituric acid;
1,3-diethyl-5-(4-ethoxycarbonylphenylamino)-methylene-barbituric acid;
1,3-diethyl-5-(4-n-propoxycarbonylphenylamino)-methylene-barbituric acid;
1,3-diethyl-5-(4-isopropoxycarbonylphenylamino)-methylene-barbituric acid;
1,3-diethyl-5-(4-n-butoxycarbonylphenylamino)-methylene-barbituric acid;
1,3-diethyl-5-(4-n-pentyloxycarbonylphenylamino)-methylene-barbituric acid;
1,3-diethyl-5-(4-n-hexyloxycarbonylphenylamino)-methylene-barbituric acid;
1,3-diethyl-5-(4-n-heptyloxycarbonylphenylamino)-methylene-barbituric acid;
1,3-diethyl-5-[4-(2-ethylhexyloxycarbonylphenylamino)]-methylene-barbituric
acid;
1,3-diethyl-5-(4-n-octadecyloxycarbonylphenylamino)-methylene-barbituric
acid;
1,3-dimethyl-5-(4-methoxyethylcarbonylphenylamino)-methylene-barbituric
acid;
1,3-dimethyl-5-(4-ethoxyethylcarbonylphenylamino)-methylene-barbituric
acid;
1,3-dimethyl-5-(4-methoxycarbomethyloxycarbonylphenylamino)-methylene-barbi
turic acid;
1,3-dimethyl-5-(4-ethoxycarbomethyloxycarbonylphenylamino)-methylene-barbit
uric acid;
1,3-diethyl-5-(4-methoxyethylcarbonylphenylamino)-methylene-barbituric
acid;
1,3-diethyl-5-(4-ethoxyethylcarbonylphenylamino)-methylene-barbituric acid;
1,3-diethyl-5-(4-methoxycarbomethyloxycarbonylphenylamino)-methylene-barbit
uric acid;
1,3-diethyl-5-(4-ethoxycarbomethyloxycarbonylphenylamino)-methylene-barbitu
ric acid, and so on.
Of the aminomethylene derivatives represented by the general formula (I)
used in the present invention, concrete examples of aminomethylene chroman
derivatives in which A in the formula (I) is (d), represented by the
formula (Id):
##STR12##
wherein R.sup.6, n and R are as defined above, include following
compounds:
3-(4-ethoxycarbonylphenylaminomethylene)chroman-2,4-dione;
3-(4-isopropoxycarbonylphenylaminomethylene)chroman-2,4-dione;
3-(4-isobutoxycarbonylphenylaminomethylene)chroman-2,4-dione;
3-(4-sec-butoxycarbonylphenylaminomethylene)chroman-2,4-dione;
3-(4-tert-butoxycarbonylphenylaminomethylene)chroman-2,4-dione;
3-(4-n-pentyloxycarbonylphenylaminomethylene)chroman-2,4-dione;
3-(4-n-hexyloxycarbonylphenylaminomethylene)chroman-2,4-dione;
3-(4-n-heptyloxycarbonylphenylaminomethylene)chroman-2,4-dione;
3-(4-n-nonyloxycarbonylphenylaminomethylene)chroman-2,4-dione;
3-(4-n-decyloxycarbonylphenylaminomethylene)chroman-2,4-dione;
3-(4-n-undecyloxycarbonylphenylaminomethylene)chroman-2,4-dione;
3-(4-n-dodecyloxycarbonylphenylaminomethylene)chroman-2,4-dione;
3-(4-n-tridecyloxycarbonylphenylaminomethylene)chroman-2,4-dione;
3-(4-n-tetradecyloxycarbonylphenylaminomethylene)chroman-2,4-dione;
3-(4-n-pentadecyloxycarbonylphenylaminomethylene)chroman-2,4-dione;
3-(4-n-hexadecyloxycarbonylphenylaminomethylene)chroman-2,4-dione;
3-(4-n-heptadecyloxycarbonylphenylaminomethylene)chroman-2,4-dione;
3-(4-methoxycarbonylphenylaminomethylene)chroman-2,4-dione;
3-(4-ethoxycarbonylphenylaminomethylene)chroman-2,4-dione;
3-(4-methoxyethylcarbonylphenylaminomethylene)chroman-2,4-dione;
3-(4-ethoxyethylcarbonylphenylaminomethylene)chroman-2,4-dione;
3-(4-methoxycarbonylmethyloxycarbonylphenylaminomethylene)-chroman-2,4-dion
e;
3-(4-ethoxycarbonylmethyloxycarbonylphenylaminomethylene)-chroman-2,4-dione
;
3-(4-ethoxycarbonylmethyloxycarbonylphenylaminomethylene)-chroman-2,4-dione
; and
5- or 6- or 7- or
8-methyl-3-(4-ethoxycarbonylphenylamino-methylene)chroman-2,4-dione;
5- or 6- or 7- or
8-methyl-3-(4-n-propoxycarbonylphenylaminomethylene)chroman-2,4-dione;
5- or 6- or 7- or
8-methyl-3-(4-n-butoxycarbonylphenylaminomethylene)chroman-2,4-dion;
5- or 6- or 7- or
8-ethyl-3-(4-methoxycarbonylphenylaminomethylene)chroman-2,4-dione;
5- or 6- or 7- or
8-ethyl-3-(4-ethoxycarbonylphenylaminomethylene)chroman-2,4-dione;
5- or 6- or 7- or
8-ethyl-3-(4-n-propoxycarbonylphenylaminomethylene)chroman-2,4-dione;
5- or 6- or 7- or
8-chloro-3-(4-ethoxycarbonylphenylaminomethylene)chroman-2,4-dione;
5- or 6- or 7- or
8-chloro-3-(4-n-propoxycarbonylphenylaminomethylene)chroman-2,4-dione;
5- or 6- or 7- or
8-chloro-3-(4-n-butoxycarbonylphenylaminomethylene)chroman-2,4-dione;
5- or 6- or 7- or
8-methoxy-3-(4-ethoxycarbonylphenylaminomethylene)chroman-2,4-dione;
5- or 6- or 7- or
8-methoxy-3-(4-n-propoxycarbonylphenylaminomethylene)chroman-2,4-dion;
5- or 6- or 7- or
8-methoxy-3-(4-n-butoxycarbonylphenylaminomethylene)chroman-2,4-dione;
5- or 6- or 7- or
8-acetyl-3-(4-methoxycarbonylphenylaminomethylene)chroman-2,4-dione;
5- or 6- or 7- or
8-acethyl-3-(4-ethoxycarbonylphenylaminomethylene)chroman-2,4-dione;
5- or 6- or 7- or
8-acetyl-3-(4-n-propoxycarbonylphenylaminomethylene)chroman-2,4-dione;
5- or 6- or 7- or
8-methylamino-3-(4-ethoxycarbonylphenylaminomethylene)chroman-2,4-dione;
5- or 6- or 7- or
8-methylamino-3-(4-n-propoxycarbonylphenylaminomethylene)chroman-2,4-dione
;
5- or 6- or 7- or
8-methylamino-3-(4-n-butoxycarbonylphenylaminomethylene)chroman-2,4-dione;
5- or 6- or 7- or
8-acethylamino-3-(4-methoxycarbonylphenylaminomethylene)chroman-2,4-dione;
5- or 6- or 7- or
8-acethylamino-3-(4-ethoxycarbonylphenylaminomethylene)chroman-2,4-dione;
5- or 6- or 7- or
8-acethylamino-3-(4-n-propoxycarbonylphenylaminomethylene)chroman-2,4-dion
e;
5- or 6- or 7- or
8-dimethylamino-3-(4-ethoxycarbonylphenylaminomethylene)chroman-2,4-dione;
5- or 6- or 7- or
8-dimethylamino-3-(4-n-propoxycarbonylphenylaminomethylene)chroman-2,4-dio
ne;
5- or 6- or 7- or
8-dimethylamino-3-(4-n-butoxycarbonylphenylaminomethylene)chroman-2,4-dion
e;
5- or 6- or 7- or
8-phenylamino-3-(4-methoxycarbonylphenylaminomethylene)chroman-2,4-dione;
5- or 6- or 7- or
8-phenylamino-3-(4-ethoxycarbonylphenylaminomethylene)chroman-2,4-dione;
5- or 6- or 7- or
8-phenylamino-3-(4-n-propoxycarbonylphenylaminomethylene)chroman-2,4-dione
, and so on.
Of the aminomethylene derivatives represented by the general formula (I)
used in the present invention, concrete examples of aminomethylene dioxane
derivatives in which A in the formula (I) is (e), represented by the
formula (Ie):
##STR13##
wherein R.sup.7, R.sup.8 and R are as defined above, include following
compounds:
2,2-dimethyl-5-(ethoxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione;
2,2-dimethyl-5-(4-isopropoxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-d
ione;
2,2-dimethyl-5-(4-isobutoxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-di
one;
2,2-dimethyl-5-(4-sec-butoxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-d
ione;
2,2-dimethyl-5-(4-tert-butoxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-
dione;
2,2-dimethyl-5-(4-n-pentyloxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-
dione;
2,2-dimethyl-5-(4-n-hexyloxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-d
ione;
2,2-dimethyl-5-(4-n-heptyloxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-
dione;
2,2-dimethyl-5-(4-n-nonyloxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-d
ione;
2,2-dimethyl-5-(4-n-decyloxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-d
ione;
2,2-dimethyl-5-(4-n-undecyloxycarbonylphenylaminomethylene)-1,3-dioxane-4,6
-dione;
2,2-dimethyl-5-(4-n-dodecyloxycarbonylphenylaminomethylene)-1,3-dioxane-4,6
-dione;
2,2-dimethyl-5-(4-n-tridecyloxycarbonylphenylaminomethylene)-1,3-dioxane-4,
6-dione;
2,2-dimethyl-5-(4-n-tetradecyloxycarbonylphenylaminomethylene)-1,3-dioxane-
4,6-dione;
2,2-dimethyl-5-(4-n-pentadecyloxycarbonylphenylaminomethylene)-1,3-dioxane-
4,6-dione;
2,2-dimethyl-5-(4-n-hexadecyloxycarbonylphenylaminomethylene)-1,3-dioxane-4
,6-dione;
2,2-dimethyl-5-(4-n-heptadecyloxycarbonylphenylaminomethylene)-1,3-dioxane-
4,6-dione;
2,2-diethyl-5-(4-methoxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione
;
2,2-diethyl-5-(4-ethoxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dione;
2,2-diethyl-5-(4-n-propoxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dio
ne;
2,2-diethyl-5-(4-isopropoxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-di
one;
2,2-diethyl-5-(4-n-butoxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dion
e;
2,2-diethyl-5-(4-n-pentyloxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-d
ione;
2,2-diethyl-5-(4-n-hexyloxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-di
one;
2,2-diethyl-5-(4-n-heptyloxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-d
ione;
2,2-diethyl-5-[4-(2-ethylhexyloxycarbonylphenylaminomethylene)]-1,3-dioxane
-4,6-dione;
2,2-diethyl-5-(4-n-octadecyloxycarbonylphenylaminomethylene)-1,3-dioxane-4,
6-dione;
2,2-dimethyl-5-(4-methoxyethylcarbonylphenylaminomethylene)-1,3-dioxane-4,6
-dione;
2,2-dimethyl-5-(4-ethoxyethylcarbonylphenylaminomethylene)-1,3-dioxane-4,6-
dione;
2,2-dimethyl-5-(4-methoxycarbomethyloxycarbonylphenylaminomethylene)-1,3-di
oxane-4,6-dione;
2,2-dimethyl-5-(4-ethoxycarbomethyloxycarbonylphenylaminomethylene)-1,3-dio
xane-4,6-dione;
2,2-diethyl-5-(4-methoxyethylcarbonylphenylaminomethylene)-1,3-dioxane-4,6-
dione;
2,2-diethyl-5-(4-ethoxyethylcarbonylphenylaminomethylene)-1,3-dioxane-4,6-d
ione;
2,2-diethyl-5-(4-methoxycarbomethyloxycarbonylphenylaminomethylene)-1,3-dio
xane-4,6-dione;
2,2-diethyl-5-(4-ethoxycarbomethyloxycarbonylphenylaminomethylene)-1,3-diox
ane-4,6-dione, and so on.
Of the starting materials employed in the manufacture of the compounds
represented by the general formula (I), the compounds of formula (II) are
concretely illustrated below.
The starting materials employed in the manufacture of the compounds of
formula (Ia) are represented by the formula (IIa'):
##STR14##
and include following compounds as concrete examples:
1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione,
5,5-diethyl-1,3-cyclohexanedione, 5,5-di-n-propyl-1,3-cyclohexanedione,
5,5-di-isopropyl-1,3-cyclohexanedione,
5,5-di-n-butyl-1,3-cyclohexanedione, 5,5-di-isobutyl-1,3-cyclohexanedione,
5,5-di-sec-butyl-1,3-cyclohexanedione,
5,5-di-n-pentyl-1,3-cyclohexanedione, 5,5-di-n-hexyl-1,3-cyclohexanedione,
5,5-di-n-heptyl-1,3-cyclohexanedione, 5,5-di-n-octyl-1,3-cyclohexanedione,
5,5-diphenyl-1,3-cyclohexanedione, 5,5-dibenzyl-1,3-cyclohexanedione,
5,5-dicyclohexyl-1,3-cyclohexanedione,
5,5-di-o-tolyl-1,3-cyclohexanedione, 5,5-di-m-tolyl-1,3-cyclo-hexanedione,
5,5-di-p-tolyl-1,3-cyclohexanedione, 5,5-di-o-anisyl-1,3-cyclohexanedione,
5,5-di-m-anisyl-1,3-cyclohexanedione,
5,5-di-p-anisyl-1,3-cyclohexanedione, 5,5-di-o-chlorophenyl-1,3-cyclohexan
edione, 5,5-di-m-chlorophenyl-1,3-cyclo-hexanedione,
5,5-di-p-chlorophenyl-1,3-cyclohexanedione,
5,5-di-o-bromophenyl-1,3-cyclohexanedione,
5,5-di-m-bromophenyl-1,3-cyclohexanedione,
5,5-di-p-bromophenyl-1,3-cyclohexanedione,
5,5-di-(2-methylcyclohexyl)-1,3-cyclohexanedione,
5,5-di-(3-methylcyclohexyl)-1,3-cyclohexanedione,
5,5-di-(4-methylcyclohexyl)-1,3-cyclohexanedione and so on.
The starting materials employed in the manufacture of the compounds of
formula (Ib) are represented by the formula (IIb'):
##STR15##
and include following compounds as concrete examples:
4-hydroxy-6-methyl-2-pyrone, 4-hydroxy-6-ethyl-2-pyrone,
4-hydroxy-6-n-propyl-2-pyrone, 4-hydroxy-6-isopropyl-2-pyrone,
4-hydroxy-6-n-butyl-2-pyrone, 4-hydroxy-6-isobutyl-2-pyrone,
4-hydroxy-6-sec-butyl-2-pyrone, 4-hydroxy-6-n-pentyl-2-pyrone,
4-hydroxy-6-n-hexyl-2-pyrone, 4-hydroxy-6-n-heptyl-2-pyrone,
4-hydroxy-6-n-octyl-2-pyrone, 4-hydroxy-6-(2-ethylhexyl)-2-pyrone,
4-hydroxy-6-cyclopentyl-2-pyrone, 4-hydroxy-6-cyclohexyl-2-pyrone,
4-hydroxy-6-allyl-2-pyrone, 4-hydroxy-6-benzyl-2-pyrone,
4-hydroxy-6-phenylethyl-2-pyrone, 4-hydroxy-6-phenyl-propyl-2-pyrone,
4-hydroxy-6-phenyl-2-pyrone, 4-hydroxy-6-o-tolyl-2-pyrone,
4-hydroxy-6-m-tolyl-2-pyrone, 4-hydroxy-6-p-tolyl-2-pyrone,
4-hydroxy-6-o-chlorophenyl-2-pyrone, 4-hydroxy-6-m-chlorophenyl-2-pyrone,
4-hydroxy-6-p-chlorophenyl-2-pyrone, 4-hydroxy-6-o-bromophenyl-2-pyrone,
4-hydroxy-6-m-bromophenyl-2-pyrone, 4-hydroxy-6-p-bromophenyl-2-pyrone,
4-hydroxy-6-o-anisyl-2-pyrone, 4-hydroxy-6-m-anisyl-2-pyrone,
4-hydroxy-6-p-anisyl-2-pyrone, 4-hydroxy-6-o-phenethyl-2-pyrone,
4-hydroxy-6-m-phenethyl-2-pyrone, 4-hydroxy-6-p-phenethyl-2-pyrone and so
on.
The starting materials employed in the manufacture of the compounds of
formula (Ic) are represented by the formula (IIc'):
##STR16##
and include following compounds as concrete examples: barbituric acid,
1,3-dimethylbarbituric acid, 1,3-diethylbarbituric acid,
1,3-di-n-propylbarbituric acid, 1,3-di-iso-propylbarbituric acid,
1,3-di-n-butylbarbituric acid, 1,3-di-isobutylbarbituric acid,
1,3-di-sec-butylbarbituric acid, 1,3-di-n-pentylbarbituric acid,
1,3-di-n-hexylbarbituric acid, 1,3-di-n-heptylbarbituric acid,
1,3-di-n-octylbarbituric acid, 1,3-diphenylbarbituric acid,
1,3-dibenzylbarbituric acid, 1,3-dicyclohexylbarbituric acid,
1,3-di-o-tolylbarbituric acid, 1,3-di-m-tolylbarbituric acid,
1,3-di-p-tolylbarbituric acid, 1,3-di-o-anisylbarbituric acid,
1,3-di-m-anisylbarbituric acid, 1,3-di-p-anisylbarbituric acid,
1,3-di-o-chlorophenylbarbituric acid, 1,3-di-m-chlorophenylbarbituric
acid, 1,3-di-p-chlorophenylbarbituric acid, 1,3-di-o-bromophenylbarbituric
acid, 1,3-di-m-bromophenylbarbituric acid, 1,3-di-allylbarbituric acid,
1,3-di-(2-methylcyclohexyl)barbituric acid,
1,3-di-(3-methylcyclohexyl)barbituric acid,
1,3-di-(4-methylcyclohexyl)barbituric acid and so on.
The starting materials employed in the manufacture of the compounds of
formula (Id) are represented by the formula (IId'):
##STR17##
and include following compounds as concrete examples: 4-hydroxycoumarin,
4,5-dihydroxycoumarin, 4,6-dihydroxycoumarin, 4,7-dihydroxycoumarin,
4-hydroxy-5-methoxycoumarin, 4-hydroxy-6-methoxycoumarin,
4-hydroxy-7-methoxycoumarin, 4-hydroxy-5-methylcoumarin,
4-hydroxy-6-methylcoumarin, 4-hydroxy-7-methylcoumarin,
4-hydroxy-5-methoxycarbonylcoumarin, 4-hydroxy-6-methoxycarbonylcoumarin,
4-hydroxy-7-methoxycarbonylcoumarin, 4-hydroxy-5-ethoxycarbonylcoumarin,
4-hydroxy-6-ethoxycarbonylcoumarin, 4-hydroxy-7-ethoxycarbonylcoumarin,
4-hydroxy-5-acetylcoumarin, 4-hydroxy-6-acetylcoumarin,
4-hydroxy-7-acetylcoumarin, 4-hydroxy-5-aminocoumarin,
4-hydroxy-6-aminocoumarin, 4-hydroxy-7-aminocoumarin,
4-hydroxy-5-dimethylaminocoumarin, 4-hydroxy-6-dimethylaminocoumarin,
4-hydroxy-7-dimethylaminocoumarin, 4-hydroxy-5-diethylaminocoumarin,
4-hydroxy-6-diethylaminocoumarin, 4-hydroxy-7-diethylaminocoumarin,
4-hydroxy-5-di-n-propylaminocoumarin,
4-hydroxy-6-di-n-propylaminocoumarin, 4-hydroxy-7-di-n-propylaminocoumarin
, 4-hydroxy-5-di-n-butylaminocoumarin, 4-hydroxy-6-di-n-butylaminocoumarin,
4-hydroxy-7-di-n-butylaminocoumarin, 4-hydroxy-5-methylaminocoumarin,
4-hydroxy-6-methylaminocoumarin, 4-hydroxy-7-methylaminocoumarin,
4-hydroxy-5-ethylaminocoumarin, 4-hydroxy-6-ethylaminocoumarin,
4-hydroxy-7-ethylaminocoumarin, 4-hydroxy-5-phenylaminocoumarin,
4-hydroxy-6-phenylaminocoumarin, 4-hydroxy-7-phenylaminocoumarin,
4-hydroxy-5-chlorocoumarin, 4-hydroxy-6-chlorocoumarin,
4-hydroxy-7-chlorocoumarin, 4-hydroxy-5-bromocoumarin,
4-hydroxy-6-bromocoumarin, 4-hydroxy-7-bromocoumarin and so on.
The starting materials employed in the manufacture of the compounds of
formula (Ie) are represented by the formula (IIe'):
##STR18##
and include following compounds as concrete examples:
2,2-dimethy-1,3-dioxane-4,6-dione, 2,2-diethy-1,3-dioxane-4,6-dione,
2,2-di-n-propyl-1,3-dioxane-4,6-dione,
2,2-di-isopropyl-1,3-dioxane-4,6-dione,
2,2-di-n-butyl-1,3-dioxane-4,6-dione,
2,2-di-isobutyl-1,3-dioxane-4,6-dione,
2,2-di-sec-butyl-1,3-dioxane-4,6-dione,
2,2-di-n-pentyl-1,3-dioxane-4,6-dione,
2,2-di-n-hexyl-1,3-dioxane-4,6-dione,
2,2-di-n-heptyl-1,3-dioxane-4,6-dione,
2,2-di-n-octyl-1,3-dioxane-4,6-dione,
2,2-di-(2-ethylhexyl)-1,3-dioxane-4,6-dione,
2,2-dicyclopentyl-1,3-dioxane-4,6-dione,
2,2-dicyclohexyl-1,3-dioxane-4,6-dione,
2,2-diphenyl-1,3-dioxane-4,6-dione, 2,2-dibenzyl-1,3-dioxane-4,6-dione,
2,2-diphenylethyl-1,3-dioxane-4,6-dione,
2,2-diphenylpropyl-1,3-dioxane-4,6-dione,
2,2-di-o-anisyl-1,3-dioxane-4,6-dione,
2,2-di-m-anisyl-1,3-dioxane-4,6-dione,
2,2-di-p-anisyl-1,3-dioxane-4,6-dione,
2,2-di-o-phenethyl-1,3-dioxane-4,6-dione,
2,2-di-m-phenethyl-1,3-dioxane-4,6-dione,
2,2-di-p-phenethyl-1,3-dioxane-4,6-dione,
2,2-di-o-chlorophenyl-1,3-dioxane-4,6-dione,
2,2-di-m-chlorophenyl-1,3-dioxane-4,6-dione,
2,2-di-p-chlorophenyl-1,3-dioxane-4,6-dione,
2,2-di-o-bromophenyl-1,3-dioxane-4,6-dione,
2,2-di-m-bromophenyl-1,3-dioxane-4,6-dione,
2,2-di-p-bromophenyl-1,3-dioxane-4,6-dione,
2,2-di-o-tolyl-1,3-dioxane-4,6-dione,
2,2-di-m-tolyl-1,3-dioxane-4,6-dione, 2,2-di-p-tolyl-1,3-dioxane-4,6-dione
and so on.
The compounds of formula (III) described above which are another starting
materials employed in the manufacture of the compounds of formula (I),
include following compounds as concrete examples: methyl
N-formylaminobenzoate, ethyl N-formylaminobenzoate, n-propyl
N-formylaminobenzoate, isopropyl N-formylaminobenzoate, n-butyl
N-formylaminobenzoate, isobutyl N-formylaminobenzoate, sec-butyl
N-formylaminobenzoate, tert-butyl N-formylaminobenzoate, n-pentyl
N-formylaminobenzoate, n-hexyl N-formylaminobenzoate, n-heptyl
N-formylaminobenzoate, n-octyl N-formylaminobenzoate, 2-ethylhexyl
N-formylaminobenzoate, n-nonyl N-formylaminobenzoate, n-nonyl
N-formylaminobenzoate, n-decyl N-formylaminobenzoate, n-undecyl
N-formylaminobenzoate, n-dodecyl N-formylaminobenzoate, n-tetradecyl
N-formylaminobenzoate, n-pentadecyl N-formylaminobenzoate, n-hexadecyl
N-formylaminobenzoate, n-heptadecyl N-formylaminobenzoate, n-octadecyl
N-formylaminobenzoate, n-nanodecyl N-formylaminobenzoate, benzyl
N-formylaminobenzoate, phenethyl N-formylaminobenzoate, phenyl-propyl
N-formylaminobenzoate, phenyl N-formylaminobenzoate, o-anisyl
N-formylaminobenzoate, m-anisyl N-formylaminobenzoate, p-anisyl
N-formylaminobenzoate, o-tolyl N-formylaminobenzoate, m-tolyl
N-formylaminobenzoate, p-tolyl N-formylaminobenzoate, o-phenethyl
N-formylaminobenzoate, m-phenethyl N-formylaminobenzoate, p-phenethyl
N-formylaminobenzoate, cyclopentyl N-formylaminobenzoate, cyclohexyl
N-formylaminobenzoate, methoxyethyl N-formylaminobenzoate, ethoxyethyl
N-formylaminobenzoate, methoxycarbonylmethyl N-formylaminobenzoate,
ethoxycarbonylmethyl N-formylaminobenzoate and so on.
Examples of antioxidants which can be added in addition to compounds
according to the present invention include following compounds:
2,6-di-tert-butyl-4-methylphenol;
2-tert-butyl-4,6-dimethylphenol;
2,6-di-tert-butyl-4-ethylphenol;
2,6-di-tert-butyl-4-n-butylphenol;
2,6-di-tert-butyl-4-isobutylphenol;
2,6-di-cyclopentyl-4-methylphenol;
2-(.alpha.-methylcyclohexyl)-4,6-dimethylphenol;
2,6-dioctadecyl-4-methylphenol;
2,4,6-tricyclohexylphenol;
2,6-dinonyl-4-methyphenol;
2,6-di-tert-butyl-4-methoxymethylphenol;
2,4-dimethyl-6-(1'-methyl-undeca-1'-yl)-phenol;
2,4-dimethyl-6-(1'-methyl-heptadeca-1'-yl)-phenol;
2,4-dimethyl-6-(1'-methyl-trideca-1'-yl)-phenol and mixture thereof;
2,4-di-octylthiomethyl-6-tert-butylphenol;
2,4-di-octylthiomethy-6-methylphenol;
2,4-di-octylthiomethy-6-ethylphenol;
2,6-di-dodecylthiomethyl-4-nonylphenol and mixutre thereof;
2,6-di-tert-butyl-4-methoxyphenol;
2,5-di-tert-butylhydroquinone;
2,5-di-tert-amylhydroquinone;
2,6-diphenyl-4-octadecyloxyphenol;
2,6-di-tert-butylhydroquinone;
2,5-di-tert-butyl-4-hydroxyanisole;
3,5-di-tert-butyl-4-hydroxyanisole;
3,5-di-tert-butyl-4-hydroxyphenylstearate;
bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate and mixture thereof;
2,4-bis-octylmercapt-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-trizine;
2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-trizine;
2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine;
2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine;
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate;
1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-isocyanurate;
2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine;
1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-tria
zine;
1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)-isocyanurate or the like; and
2,2'-methylenebis(6-tert-butyl-4-methylphenol);
2,2'-methylenebis(6-tert-butyl-4-ethylphenol);
2,2'-ethylidenebis(4,6-di-tert-butylphenol);
2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol);
4,4'-methylenebis(2,6-di-tert-butylphenol);
4,4'-methylenebis(6-tert-butyl-2-methylphenol);
1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane;
ethylene glycol bis[3,3'-bis(3'-tert-butyl-4'-hydroxyphenyl)butylate]or the
like; and
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene;
1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene;
2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol or the like.
Examples of light stabilizing agents which can be added in addition to
compounds according to the present invention include following compounds:
2-(2'-hydroxy-5'-methylphenyl)benzotriazole,
2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole,
2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole,
2-[2'-hydroxy-5'-(1,1,3,3-tetra-methylbutyl)phenyl]benzotriazole,
2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-methyphenyl)-5-chlorobenzotriazole,
2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole,
2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole,
2-[3'-tert-butyl-2'-hydroxy-5'-(2'-octyloxycarbonylethylphenyl)-5-chlorobe
nzotriazole or the like;
4-hydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-,
4-benzyloxy-, 4,2',4'-trihydroxy-, 2'-hydroxy-4,4'-dimethoxy- or
4-(2-ethylhexyloxy)-2-hydroxybenzophenone derivatives or the like;
4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate,
dibenzoyl resorcinol, bis(4-tert-butylbenzoyl resorcinol,
2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl
3,5-di-tert-butyl-4-hydroxybenzoate or the like; ethyl
.alpha.-cyano-.beta., .beta.-diphenylacrylate, isooctyl
.alpha.-cyano-.beta., .beta.-diphenylacrylate, methyl
.alpha.-carbomethoxycinnamate, methyl
.alpha.-cyano-.beta.-methyl-p-methoxycinnamate or the like;
bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,
bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,
bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)adipate or the like;
4,4'-di-octyloxyoxanilide, 2,2'-diethoxyoxyoxanilide,
2,2'-di-octyloxy-5,5'-di-tert-butyloxanilide,
2,2'-di-dodecyloxy-5,5'-di-tert-butyloxanilide,
2-ethoxy-2'-ethyloxanilide, N,N'-bis-(3-dimethylaminopropyl)oxanilide,
2-ethoxy-5-tert-butyl-2'-ethoxyoxanilide or the like;
2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,
2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,
2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethyl-phenyl)-1,3,5-triazine,
2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine
, 2-(2-hydroxy-4-dodecyloxy-phenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triaz
ine or the like.
Example of metal inactivators which can be added in addition to compounds
according to the present invention include, N,N'-diphenyloxamide,
N-salcylal-N'-salicyloyl-hydrazine, N,N'-bis(salicyloyl)hydrazine,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,
3-salicylolyamino-1,2,3-triazole, bis(benzylidene)oxalic acid hydrazide,
isophthalic acid dihydrazide, N,N'-diacetal-adipic acid dihydrazide,
N,N'-bis-salicyloyloxalic acid dihydrazide,
N,N'-bis(salicyloyl)thiopropionic acid dihidrazide or the like.
Examples of peroxide scavengers which can be added in addition to compounds
according to the present invention include, dilauryl thiodipropionate,
distearyl thiodipropionate, dimyristyl thiodipropionate or ditridecyl
thiodipropionate, 2-mercaptobenzimidazole,
pentaerythritoltetrakis(dodecyl-mercapto)propionate or the like.
The aminomethylene derivatives of the present invention have preferred
chracteriscits, that they have much higher ultraviolet absorption compared
to that of conventionally known ultraviolet absorbent for UV-A range, as
the maximum absorption range of aminomethylene cyclohexane derivatives of
the present invention represented by the general formula (I) in which A is
(a) is 340 to 360 nm, the maximum absorption range of aminomethylene
pyrone derivatives of the present invention represented by the general
formula (I) in which A is (b) is 340 to 360 nm, and the maximum absorption
range of aminomethylene barbituric acid derivatives of the present
invention represented by the general formula (I) in which A is (c) is 340
to 360 nm, the maximum absorption range of aminomethylene chroman
derivatives of the present invention represented by the general formula
(I) in which A is (d) is 340 to 380 nm, and the maximum absorption range
of aminomethylene dioxane derivatives of the present invention represented
by the general formula (I) in which A is (e) is 330 to 350 nm, and the
present compounds have lower irritability and no other toxicity, higher
compatibility to other cosmetic bases, and smaller percutaneous
absorption.
The base for skin ointment which is also the cosmetic materials according
to the present invention can be any that is inactive to above described
aminomethylene derivatives (I), and can be solid, liquid, emulsion,
foaming solution, gel or the like. Examples of the cosmetic base of the
present invention include olive oil, tsubaki oil, cotton seed oil, castor
oil, soybean oil, coconut oil, cacao butter, lanoline, bees wax, carnauba
wax, hardened oil, stearic acid, palmitic acid, myristic acid, ascorbic
acid, behenic acid, and esters or metal salts thereof, higher alcohol
including decylethyl, oleyl, lauryl, cetyl or stearyl alcohol. Examples of
other base include synthetic oil such as squalene monostearic acid
glyceride, synthetic polyether oils, sorbitan monooleate, lanoline and
hydrogenated forms thereof and squalenes; mineral oil such as paraffin,
petrolatum, liquid paraffin, microcrystal wax or the like. Further, other
examples of base which can be used include silicone oil, polyethers,
dialkylsiloxanes, fine powders of starch or talc, carbohydrate with lower
boiling point or carbohydrate containing halogen both of which are used as
a switchsbout type power propellant.
Examples of the humectants include glycerin, propylene glycol, sorbitol,
polyethylene glycol, sodium pyrrolidone carboxylate or the like. Examples
of sticking agents include polyvinyl alcohol, sodium salt of carboxymethyl
cellulose, sodium alginate, propylene glycol ester or the like.
Examples of the preservatives include benzoic acid, sorbic acid,
dehydroacetic acid, p-hydroxy benzoic acid esters or the like. Examples of
the solvent include ethanol, acetone, acetates, isopropanol or the like.
Examples of ultraviolet absorbent which can be combinedly used include
benzotriazoles such as 2-(2'-hydroxy-5'-methylphenyl)benzotriazole,
2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole,
2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole,
2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole,
2-(2'-hydroxy-4'-n-octoxyphenyl)-benzotriazole or the like;
benzophenones such as 2-hydroxy-4-methoxy-2'-carboxybenzophenone,
2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone,
2,2'-dihydroxy-4,4'-dimethoxybenzophenone,
2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone,
2-hydroxy-4-methoxybenzophenone-5-sulfonic acid,
2-hydroxy-4-octadecyloxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone,
2-hydroxy-4-dodecyloxybenzophenone,
2-hydroxy-4-(2-hydroxy-3-methacryloxy)propoxybenzophenone or the like;
compounds belonging to benzoic acid family such as methyl o-benzoyl
benzoate, p-aminobenzoic acid, glyceryl p-aminobenzoate, ethyl
p-aminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, octyl
p-dimethylaminobenzoate, ethyl 4-bis(hydroxybutyl)aminobenzoate, methyl
o-aminobenzoate or the like; compounds belonging to cinnamic acid family
such as benzyl cinnamate, p-methoxycinnamic acid diethanolamine,
2-ethylhexyl p-methoxycinnamate, isopropyl p-methoxycinnamate or the like;
and
other acid esters such as gallic acid triesters, 2-ethylhexyl salicylate,
3,3,5-trimethylcyclohexyl salicylate, salicylic acid triethanolamine,
p-butylphenyl salicylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate,
2-ethylhexyl 3-cyano-3,3-diphenylacrylate or the like.
Cosmetic materials containing above described aminomethylene derivatives
(I) of the present invention are produced by adding the same to above
described known cosmetic base using an ordinary method to prepare cream,
solution, oil, spray, stick, emulsion, foundation, and ointment.
Formulation ratio of above described aminomethylene derivatives (I) in the
cosmetic materials of the present invention can differ according to the
form of use and is not limited, and can be any amount that is effective,
and in general the aminomethylene derivatives is added to the composition
at a ratio of 0.1 to 20 weight %, preferably 0.5 to 5 weight %. Further
above described aminomethylene derivatives (I) of the present invention
can be added alone but more preferable effect can be obtained by combining
with other UV-B absorbents, UV-A absorbents or the like, when it is used
for ordinary sunscreen cosmetics. Above described aminomethylene
derivatives (I) of the present invention can be used by combining with
many other additives. Examples of suitable additives include emulsion of
W/O type and O/W type. Regarding emulsifiers, commercially available
emulsifiers including polyglycerin fatty acid esters, polyoxyethylene
lanolin derivatives, polyoxyethylene sorbitan fatty acid esters,
polyoxyethylene polyoxypropylene alkylethers, polyoxyethylene-sorbitol
fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid
esters or the like. Further, thickeners including ethylcellulose,
polyacrylic acid, gelatin, agar or the like can be added if necessary. In
addition, perfumes, humectants, emulsifying agents, medically active
ingredients and others may be optionally added.
EXAMPLES
The present invention will be further described with reference to the
following examples of synthesis of the compounds of the invention, and
cosmetic materials and polymer composition comprising said compounds,
however these examples are intended to show some preferred embodiments and
are not to be constructed to limit the scope of the invention.
Example 1
Synthesis of 2-(4-methoxycarbonylphenylamino)-methylene-1,3-cyclohexadione
[compound represented by the general formula (I) of which A is (a),
R.sup.1 =R.sup.2 =hydrogen atom and R=methyl]
After stirring suspension containing 0.20 mol of 1,3-cyclohexanedione, 0.50
mol of 4-methoxycarbonyl-N-formanilide and 25 ml of toluene, 0.50 mol of
phosphorus oxychloride is added to the suspension over 15 minutes. During
the addition, temperature is maintained at 45.degree. C. or lower. The
suspension is further stirred for 10 minutes, then 250 ml of hot solution
of toluene containing 0.48 mol of 1,3-cyclohexanedione is added to at 60
to 65.degree. C., over 45 minutes. The reaction mixture is constantly
stirred and allowed to cool to room temperature, and reaction is
terminated by adding the reaction mixture dropwise into 600 ml of 15%
sodium hydroxide solution. Obtained organic layer is being washed with 200
ml of saturated aqueous solution of sodium chloride. The organic layer is
fractionated, allowed to dry on anhydrous sodium sulfate, filtrated and
concentrated to obtaine crude product.
Purified product having the melting point of 198 to 199.degree. C. is
obtained through recrystalization from ethanol.
Mass spectrum: m/z 274(M++1, 17%), 273(M+, 96), 242(16), 217(58), 202(24),
144(25), 123(19), 89(10);
Ultraviolet absorption spectrum (ethanol): .lambda. max(nm) 358 (.epsilon.
max 38,000).
Example 2
Synthesis of
2-(4-n-propoxycarbonylphenylamino)-methylene-1,3-cyclohexadione [compound
represented by the general formula (I) of which A is (a), R.sup.1 =R.sup.2
=hydrogen atom and R=n-propyl]
Title compound was synthesized from 1,3-cyclohexanedione and
4-n-propyloxycarbonyl-N-formanilide using the same reaction conditions and
after-treatment used in EXAMPLE 1.
Purified product having the melting point of 147.5 to 148.5.degree. C. was
obtained through recrystalization from ethanol.
Mass spectrum: m/z 302(M++1, 25%), 301(M+, 100), 259(18), 245(52), 242(37),
230(18), 203(12), 188(10), 144(26), 123(22), 89(10);
Ultraviolet absorption spectrum (ethanol): .lambda. max(nm) 358 (.epsilon.
max 34,000).
Example 3
Synthesis of 2-(4-n-butoxycarbonylphenylamino)-methylene-1,3-cyclohexadione
[compound represented by the general formula (I) of which A is (a),
R.sup.1 =R.sup.2 =hydrogen atom and R=n-butyl]
Title compound was synthesized from 1,3-cyclohexanedione and
4-n-butyloxycarbonyl-N-formanilide using the same reaction conditions and
after-treatment used in EXAMPLE 1.
Purified product having the melting point of 144.5 to 146.degree. C. was
obtained through recrystalization from ethanol.
Mass spectrum: m/z 316(M++1, 20%), 315(M+, 100), 260(12), 259(70), 242(32),
203(13), 144(15), 123(13);
Ultraviolet absorption spectrum (ethanol): .lambda. max(nm) 358 (.epsilon.
max 33,800).
Example 4
Synthesis of
2-(4-n-octadecyloxycarbonylphenylamino)-methylene-1,3-cyclohexadione
[compound represented by the general formula (I) of which A is (a),
R.sup.1 =R.sup.2 =hydrogen atom and R=n-octadecyl]
Title compound was synthesized from 1,3-cyclohexanedione and
4-n-octadecyloxycarbonyl-N-formanilide using the same reaction conditions
and after-treatment used in EXAMPLE 1.
Purified product having the melting point of 114.5 to 115.5.degree. C. was
obtained through recrystalization from ethanol.
Mass spectrum: m/z 512(M++1, 17%), 511(M+, 48), 389(22), 260(14), 242(11),
215(12), 138(26), 137(100), 120(31);
Ultraviolet absorption spectrum (ethanol): .lambda. max(nm) 363 (.epsilon.
max 27,000).
Example 5
Synthesis of
5,5-dimethyl-2-(4-methoxycarbonylphenylamino)-methylene-1,3-cyclohexadione
[compound represented by the general formula (I) of which A is (a),
R.sup.1 =R.sup.2 =methyl and R=methyl]
Title compound was synthesized from dimedone and
4-methoxycarbonyl-N-formanilide using the same reaction conditions and
after-treatment used in EXAMPLE 1.
Purified product having the melting point of 193 to 194.5.degree. C. was
obtained through recrystalization from ethanol.
Mass spectrum: m/z 302(M++1, 20%), 301(M+, 100), 270(12), 217(65), 202(16),
151(10), 144(19);
Ultraviolet absorption spectrum (ethanol): .lambda. max(nm) 358 (.epsilon.
max 50,000).
Example 6
Synthesis of
5,5-dimethyl-2-(4-n-propoxycarbonylphenylamino)-methylene-1,3-cyclohexadio
ne [compound represented by the general formula (I) of which A is (a),
R.sup.1 =R.sup.2 =methyl and R=n-propyl]
Title compound was synthesized from dimedone and
4-n-propyloxycarbonyl-N-formanilide using the same reaction conditions and
after-treatment used in EXAMPLE 1.
Purified product having the melting point of 182 to 183.degree. C. was
obtained through recrystalization from ethanol.
Mass spectrum: m/z 330(M++1, 21%), 329(M+, 100), 270(21), 245(43), 144(13);
Ultraviolet absorption spectrum (ethanol): .lambda. max(nm) 358 (.epsilon.
max 49,000).
Example 7
Synthesis of
5,5-dimethyl-2-(4-n-butoxycarbonylphenylamino)-methylene-1,3-cyclohexadion
e [compound represented by the general formula (I) of which A is (a),
R.sup.1 =R.sup.2 =methyl and R=n-butyl]
Title compound was synthesized from dimedone and
4-n-butyloxycarbonyl-N-formanilide using the same reaction conditions and
after-treatment used in EXAMPLE 1.
Purified product having the melting point of 169.5 to 170.degree. C. was
obtained through recrystalization from ethanol.
Mass spectrum: m/z 344(M++1, 23%), 343(M+, 100), 287(32), 270(23), 259(34),
203(12), 144(13);
Ultraviolet absorption spectrum (ethanol): .lambda. max(nm) 358
(.epsilon.max 48,700).
Example 8
Synthesis of
5,5-dimethyl-2-[4-(2-ethylhexyloxycarbonylphenylamino)]-methylene-1,3-cycl
ohexadione [compound represented by the general formula (I) of which A is
(a), R.sup.1 =R.sup.2 =methyl and R=2-ethylhexyl]
Title compound was synthesized from dimedone and
4-(2-ethylhexyloxycarbonyl)-N-formanilide using the same reaction
conditions and after-treatment used in EXAMPLE 1.
Purified product having the melting point of 123.5 to 124.5.degree. C. was
obtained through recrystalization from ethanol.
Mass spectrum: m/z 400(M++1, 8%), 399(M+, 39), 288(22), 287(100), 270(26),
203(27);
Ultraviolet absorption spectrum (chloroform): .lambda. max(nm) 364
(.epsilon. max 53,600).
Example 9
Synthesis of
5,5-dimethyl-2-(4-n-octadecyloxycarbonylphenylamino)-methylene-1,3-cyclohe
xadione [compound represented by the general formula (I) of which A is (a),
R.sup.1 =R.sup.2 =methyl and R=n-octadecyl]
Title compound was synthesized from dimedone and
4-n-octadecyloxycarbonyl-N-formanilide using the same reaction conditions
and after-treatment used in EXAMPLE 1.
Purified product having the melting point of 115 to 116.5.degree. C. was
obtained through recrystalization from ethanol.
Mass spectrum: m/z 540(M++1, 39%), 539(M+, 100), 525(12), 524(32), 288(28),
271(15), 270(25), 243(36), 137(17), 120(19);
Ultraviolet absorption spectrum (chloroform): .lambda. max(nm) 363
(.epsilon. max 40,000).
Example 10
Practical examples of formulation of skin ointment according to the present
invention hereunder will be described.
According to the formulation listed in Table 1, a cosmetic liquid
containing the compound according to EXAMPLE 8, that is
5,5-dimethyl-2-[4-(2-ethylhexyloxycarbonylphenylamino)]-methylene-1,3-cycl
ohexadione and as control cosmetic liquids, cosmetic liquids containing
compound of Control 1, that is 2,2',4,4'-tetrahydroxybenzophenone, and
compound of Control 2, that is 2-ethylhexyl p-methoxycinnamate,
respectively, were prepared.
TABLE 1
______________________________________
Composition EXAMPLE 10 Control 1 Control 2
______________________________________
ethanol 8.0 8.0 8.0
glycerin 2.0 2.0 2.0
citric acid 0.02 0.02 0.02
sodium citrate 0.1 0.1 0.1
methylparaben 0.05 0.05 0.05
POE hardened caster oil 0.5 0.5 0.5
perfume some some some
compound of EXAMPLE 8 1.0 -- --
compound of Control 1 -- 1.0 --
compound of Control 2 -- -- 1.0
propylene glycol 7.0 7.0 7.0
purified water rest rest rest
______________________________________
Control 1 exhibited pale yellow and was not suitable for cosmetic liquid.
Confirmation of Sunscreening Effect
Cosmetic liquid according to EXAMPLE 10 in which compound produced
according to EXAMPLE 8 and that of Control 2 were, respectively, applied
on the skin and their effect at practical use in beach was tested. On each
of right or left half area of the back of ten respective male and female,
each sample solution was applied, and the degree of suntan was examined
and obtained results was listed in Table 2. According to the degree of
suntan, results were estimated based on the following estimation criteria.
______________________________________
Estimation Criteria
______________________________________
no rash .smallcircle.
slight rash .DELTA.
severe rash .times.
______________________________________
TABLE 2
______________________________________
Estimation Area applied with
Area applied
criteria EXAMPLE 10 with Control 2
______________________________________
.smallcircle.
17 12
.DELTA. 3 6
.DELTA. - .times. 0 2
.times. 0 0
Frequency of No itching 7 cases
skin trouble slight rash 1 case
______________________________________
Example 11
Light Stability Effect for Polymer Materials
Each of 0.05, 0.2 and 0.5 part by weight of sample produced according to
EXAMPLE 8 was formulated with 100 parts by weight of polyethylene powder
or polypropylene powder, mixed well using a mixer, then melted and kneaded
using a extruder having the diameter of 25 mm at cylinder temperature of
200.degree. C., and pelletized. Obtained pellets were compacted into
sheets of 0.25 mm thickness at 210.degree. C. to prepare test strips.
Obtained test strips were punched into dumbbell shapes accommodating to a
tension test. Test strip of control which did not contain light
stabilizing agent was prepared, using the above described same method, and
test strips were examined.
Using the WEL-75XS-HS-BEC model xenon sunshine long-life weatherometer
manufactured by Suga Shiken-Kiki Co. Ltd., these test strips were
light-irradiated with black panel temperature of 80.degree. C., and were
examined for lowering in tensile strength over time.
The tension test was performed at 23.+-.2.degree. C., relative humidity of
50.+-.5%, test speed of 50.+-.5.0 mm/minutes, using the DSS-5000 model
tension meter manufactured Shimadzu Seisakusho Co. Ltd. Tension strength
was calculated according to the following method.
Equation 1
Ts=S/T.multidot.W
wherein,
Ts=tension strength (kgf/mm.sup.2)
T=thickness of samples (mm)
W=wide of samples (mm)
S=maximum strength of samples (kgf)
Obtained results were as listed by Table 3. As apparent from the results
shown in Table 3, the aminomethylene cyclohexane derivatives according to
the present invention show prominent stabilizing effect (that is,
elongated time to deterioration).
TABLE 3
______________________________________
(unit: kgf)
Name of resin
200 400 600 800 1000 1200
hrs hrs hrs hrs hrs hrs
______________________________________
Polypropylene: no,
3.15 2.13 0 -- -- --
0.05 (wt%) 3.60 3.10 2.90 -- -- --
0.2 (wt%) 3.70 3.45 3.40 -- -- --
0.5 (wt%) 3.98 3.80 3.65 -- -- --
Polyethylene: no, 2.42 2.29 2.25 2.10 1.90 0
0.05 (wt%) 2.65 2.56 2.50 2.45 2.30 2.21
0.2 (wt%) 2.81 2.70 2.62 2.55 2.42 2.39
0.5 (wt%) 2.88 2.80 2.75 2.70 2.63 2.60
______________________________________
Example 12
Synthesis of
6-methyl-3-(4-methoxycarbonylphenyaminomethylene)-2H,3H,4H-pyran-2,4-dione
[compound represented by general (I) in which A is (b) and R.sup.3
=methyl, R=methyl]
Suspension containing 0.20 mol of 4-hydroxy-6-methyl-2-pyrone, 0.50 mol of
4-methoxycarbonyl-N-formanilide and 25 ml of toluene was mixed and added
with 0.50 mol of phosphorous oxychloride over 15 minutes. During the
addition temperature was maintained at 45.degree. C. or lower. The
suspension is further stirred for 10 minutes, then 250 ml of hot solution
of toluene containing 0.48 mol of 4-hydroxy-6-methyl-2-pyrone is added to
at 60 to 65.degree. C., over 45 minutes. The reaction mixture is
constantly stirred and allowed to cool to room temperature, and reaction
is terminated by adding the reaction mixture dropwise into 600 ml of 15%
sodium hydroxide solution. Obtained organic layer is being washed with 200
ml of saturated aqueous solution of sodium chloride. The organic layer is
fractionated, allowed to dry on anhydrous sodium sulfate, filtrated and
concentrated to obtain crude product.
Purified product having the melting point of 251 to 253.degree. C. is
obtained through recrystalization from dioxane.
Mass spectrum: m/z 288(M++1, 18%), 287(M+, 100), 256(15), 244(15), 202(24),
175(19), 144(41), 137(18), 116(14), 98(34), 89(14), 85(12);
Ultraviolet absorption spectrum (ethanol): .lambda. max(nm) 368 (.epsilon.
max 51,000).
Example 13
Synthesis of
6-methyl-3-(4-n-propoxycarbonylphenylaminomethylene)-2H,3H,4H-pyran-2,4-di
one [compound represented by the general formula (I) of which A is (b),
R.sup.3 =methyl and R=n-propyl]
Title compound was synthesized from 4-hydroxy-6-methyl-2-pyrone and
4-n-propyloxycarbonyl-N-formanilide using the same reaction conditions and
after-treatment used in EXAMPLE 12.
Purified product having the melting point of 199 to 200.degree. C. was
obtained through recrystalization from dioxane.
Mass spectrum: m/z 316(M++1, 22%), 315(M+, 100), 273(28), 272(13), 256(33),
230(14), 172(11), 144(27), 137(15), 98(26), 89(10), 85(10);
Ultraviolet absorption spectrum (ethanol): .lambda. max(nm) 368 (.epsilon.
max 48,300).
Example 14
Synthesis of
6-methyl-3-(4-n-butoxycarbonylphenylaminomethylene)-2H,3H,4H-pyran-2,4-dio
ne [compound represented by the general formula (I) of which A is (b),
R.sup.3 =methyl and R=n-butyl]
Title compound was synthesized from 4-hydroxy-6-methyl-2-pyrone and
4-n-butyloxycarbonyl-N-formanilide using the same reaction conditions and
after-treatment used in EXAMPLE 12.
Purified product having the melting point of 176.5 to 177.degree. C. was
obtained through recrystalization from dioxane.
Mass spectrum: m/z 330(M++1, 21%), 329(M+, 100), 274(12), 273(73), 256(33),
188(11), 172(11), 161(12), 144(26), 137(15), 98(26), 89(10), 85(10);
Ultraviolet absorption spectrum (ethanol): .lambda. max(nm) 368 (.epsilon.
max 77,900).
Example 15
Synthesis of
6-methyl-3-(4-n-octadecyloxycarbonylphenylaminomethylene)-2H,3H,4H-pyran-2
,4-dione [compound represented by the general formula (I) of which A is
(b), R.sup.3 =methyl and R=n-octadecyl]
Title compound was synthesized from 4-hydroxy-6-methyl-2-pyrone and
4-n-octadecyloxycarbonyl-N-formanilide using the same reaction conditions
and after-treatment used in EXAMPLE 12.
Purified product having the melting point of 137 to 138.5.degree. C. was
obtained through recrystalization from toluene.
Mass spectrum: m/z 525(M++1, 100%), 524(10), 496(17), 482(15), 468(19),
454(15), 440(14), 426(14), 412(12), 387(13), 385(10), 384(11), 370(11),
356(11), 342(12), 328(12), 275(14), 274(69), 273(68), 257(38), 256(56),
230(17), 229(67), 172(15), 165(11), 146(11), 144(18), 138(13), 137(32),
120(22), 117(12), 97(12), 91(19);
Ultraviolet absorption spectrum (chloroform): .lambda. max(nm) 372
(.epsilon. max 30,200).
Example 16
Synthesis of
6-methyl-3-[4-(2-ethylhexyloxycarbonylphenyl)-aminomethylene]-2H,3H,4H-pyr
an-2,4-dione [compound represented by the general formula (I) of which A is
(b), R.sup.3 =methyl and R=2-ethylhexyl]
Title compound was synthesized from 4-hydroxy-6-methyl-2-pyrone and
4-(2-etylhexyloxycarbonyl)-N-formanilide using the same reaction
conditions and after-treatment used in EXAMPLE 12.
Purified product having the melting point of 173.5 to 174.5.degree. C. was
obtained through recrystalization from toluene.
Mass spectrum: m/z 3850(M++1, 35%), 274(21), 273(100), 256(34), 188(6),
172(9), 144(8);
Ultraviolet absorption spectrum (chloroform): .lambda. max(nm) 373
(.epsilon. max 34,300).
Example 17
Practical examples of formulation of skin ointment according to the present
invention hereunder will be described.
According to the formulation listed in Table 4, a cosmetic liquid
containing the compound according to EXAMPLE 16, that is
6-methyl-3-[4-(2-ethylhexyloxycarbonylphenyl)-aminomethylene]-2H,3H,4H-pyr
an-2,4-dione and as control cosmetic liquids, cosmetic liquids containing
compound of Control 1, that is 2,2',4,4'-tetrahydroxybenzophenone, and
compound of Control 2, that is 2-ethylhexyl p-methoxycinnamate,
respectively, were prepared.
TABLE 4
______________________________________
Composition EXAMPLE 17 Control 1
Control 2
______________________________________
ethanol 8.0 8.0 8.0
glycerin 2.0 2.0 2.0
citric acid 0.02 0.02 0.02
sodium citrate 0.1 0.1 0.1
methylparaben 0.05 0.05 0.05
POE hardened caster oil 0.5 0.5 0.5
perfume some some some
compound of EXAMPLE 16 1.0 -- --
compound of Control 1 -- 1.0 --
compound of Control 2 -- -- 1.0
propylene glycol 7.0 7.0 7.0
purified water rest rest rest
______________________________________
Control 1 exhibited pale yellow and was not suitable for cosmetic liquid.
Confirmation of Sunscreening Effect
Cosmetic liquid according to EXAMPLE 17 in which compound produced
according to EXAMPLE 16 and that of Control 2 were, respectively, applied
on the skin and their effect at practical use in beach was tested. On each
of right or left half area of the back of ten respective male and female,
each sample solution was applied, and the degree of suntan was examined
and obtained results was listed in Table 5. Above described estimation
criteria was used.
TABLE 5
______________________________________
Estimation Area applied with
Area applied
criteria: EXAMPLE 17 with Control 2
______________________________________
.smallcircle.
20 12
.DELTA. 0 6
.DELTA. - .times. 0 2
.times. 0 0
Frequency of No itching 7 cases
skin trouble slight rash 1 case
______________________________________
Example 18
Light Stability Effect for Polymer Materials
Each of 0.05, 0.2 and 0.5 part by weight of sample produced according to
EXAMPLE 16 was formulated with 100 parts by weight of polyethylene powder
or polypropylene powder, mixed well using a mixer, then melted and kneaded
using a extruder having the diameter of 25 mm at cylinder temperature of
200.degree. C., and pelletized. Obtained pellets were compacted into
sheets of 0.25 mm thickness at 210.degree. C. to prepare test strips.
Obtained test strips were punched into dumbbell shapes accommodating to a
tension test. Test strip of control which did not contain light
stabilizing agent was prepared, using the above described same method, and
test strips were examined.
Using the WEL-75XS-HS-BEC model xenon sunshine long-life weatherometer
manufactured by Suga Shiken-Kiki Co. Ltd., these test strips were
light-irradiated with black panel temperature of 80.degree. C., and were
examined for lowering in tensile strength over time.
The tension test and calculation of tension strength was performed
according above described methods.
Obtained results were as listed in Table 6. As apparent from the results
shown in Table 6, the aminomethylene pyrone derivatives according to the
present invention show prominent stabilizing effect (that is, elongated
time to deterioration).
TABLE 6
______________________________________
(unit: kgf)
Name of resin
200 400 600 800 1000 1200
hrs hrs hrs hrs hrs hrs
______________________________________
Polypropylene: no,
3.15 2.13 0 -- -- --
0.05 (wt%) 3.40 3.34 2.98 -- -- --
0.2 (wt%) 3.65 3.49 3.23 -- -- --
0.5 (wt%) 3.85 3.62 3.42 -- -- --
Polyethylene: no, 2.42 2.29 2.25 2.10 1.90 0
0.05 (wt%) 2.50 2.47 2.44 2.42 2.23 2.20
0.2 (wt%) 2.58 2.50 2.49 2.44 2.37 2.31
0.5 (wt%) 2.66 2.59 2.55 2.51 2.41 2.38
______________________________________
Example 19
Synthesis of
1,3-dimethyl-5-(4-methoxycarbonylphenyl)-aminomethylene-barbituric acid
[compound represented by the general formula (I) of which A is (c),
R.sup.4 =R.sup.5 =methyl and R=methyl]
After stirring suspension containing 0.20 mol of 1,3-dimethyl barbituric
acid, 0.50 mol of 4-methoxycarbonyl-N-formanilide and 25 ml of toluene
(solvent), 0.50 mol of phosphorus oxychloride is added to the suspension
over 15 minutes. During the addition, temperature is maintained at
45.degree. C. or lower. The suspension is further stirred for 10 minutes,
then 250 ml of hot solution of toluene containing 0.48 mol of 1,3-dimethyl
barbituric acid is added to at 60 to 65.degree. C., over 45 minutes. The
reaction mixture is constantly stirred and allowed to cool to room
temperature, and reaction is terminated by adding the reaction mixture
dropwise into 600 ml of 15% sodium hydroxide solution. Obtained organic
layer is being washed with 200 ml of saturated aqueous solution of sodium
chloride. The organic layer is fractionated, allowed to dry on anhydrous
sodium sulfate, filtrated and concentrated to obtain crude product.
Purified product having the melting point of 239.5 to 240.5 t is obtained
through recrystalization from ethanol/dioxane.
Ultraviolet absorption spectrum (ethanol): .lambda. max(nm) 352, (.epsilon.
max 49,000).
Example 20
Synthesis of
1,3-dimethyl-5-(4-n-propoxycarbonylphenyl)-aminomethylene-barbituric acid
[compound represented by the general formula (I) of which A is (c),
R.sup.4 =R.sup.5 =methyl and R=n-propyl]
Title compound was synthesized from 1,3-dimethyl barbituric acid and
4-n-propyloxycarbonyl-N-formanilide using the same reaction conditions and
after-treatment used in EXAMPLE 19.
Purified product having the melting point of 150 to 151.degree. C. was
obtained through recrystalization from ethanol/dioxane.
Ultraviolet absorption spectrum (ethanol): .lambda. max(nm) 354 (.epsilon.
max 48,400).
Example 21
Synthesis of
1,3-dimethyl-5-(4-n-butoxycarbonylphenyl)-aminomethylene-barbituric acid
[compound represented by the general formula (I) of which A is (c),
R.sup.4 =R.sup.5 =methyl and R=n-butyl]
Title compound was synthesized from 1,3-dimethyl barbituric acid and
4-n-butyloxycarbonyl-N-formanilide using the same reaction conditions and
after-treatment used in EXAMPLE 19.
Purified product having the melting point of 139 to 140.degree. C. was
obtained through recrystalization from ethanol/dioxane.
Ultraviolet absorption spectrum (ethanol): .lambda. max(nm) 353 (.epsilon.
max 47,800).
Example 22
Synthesis of
1,3-dimethyl-5-(4-n-octadecyloxycarbonyl-phenyl)aminomethylene-barbituric
acid [compound represented by the general formula (I) of which A is (c),
R.sup.4 =R.sup.5 =methyl and R=n-octadecyl]
Title compound was synthesized from 1,3-dimethyl barbituric acid and
4-n-octadecyloxycarbonyl-N-formanilide using the same reaction conditions
and after-treatment used in EXAMPLE 19.
Purified product having the melting point of 116.5 to 117.5.degree. C. was
obtained through recrystalization from toluene.
Ultraviolet absorption spectrum (chloroform): .lambda. max(nm) 356
(.epsilon. max 38,800).
Example 23
Synthesis of 1,3-dimethyl-5-
{N-[4-(2-ethylhexyl)oxycarbonylphenyl]aminomethylene} barbituric acid
[compound represented by the general formula (I) of which A is (c),
R.sup.4 =R.sup.5 =methyl and R=2-ethylhexyl]
Title compound was synthesized from 1,3-dimethyl barbituric acid and
4-(2-ethylhexyl)oxycarbonyl-N-formanilide using the same reaction
conditions and after-treatment used in EXAMPLE 19.
Purified product having the melting point of 164.5 to 165.5.degree. C. was
obtained through recrystalization from toluene.
Ultraviolet absorption spectrum (ethanol): .lambda. max(nm) 356 (.epsilon.
max 40,700).
Example 24
Practical examples of formulation of skin ointment according to the present
invention hereunder will be described.
According to the formulation listed in Table 7, a cosmetic liquid
containing the compound according to EXAMPLE 23, that is 1,3-dimethyl-5-
{N-[4-(2-ethylhexyl)oxycarbonylphenyl]-aminomethylene} barbituric acid and
as control cosmetic liquids, cosmetic liquids containing compound of
Control 1, that is 2,2',4,4'-tetrahydroxybenzophenone, and compound of
Control 2, that is 2-ethylhexyl p-methoxycinnamate, respectively, were
prepared.
TABLE 71
______________________________________
Composition EXAMPLE 24 Control 1
Control 2
______________________________________
ethanol 8.0 8.0 8.0
glycerin 2.0 2.0 2.0
citric acid 0.02 0.02 0.02
sodium citrate 0.1 0.1 0.1
methylparaben 0.05 0.05 0.05
POE hardened caster oil 0.5 0.5 0.5
perfume some some some
compound of EXAMPLE 23 1.0 -- --
compound of Control 1 -- 1.0 --
compound of Control 2 -- -- 1.0
propylene glycol 7.0 7.0 7.0
purified water rest rest rest
______________________________________
Control 1 exhibited pale yellow and was not suitable for cosmetic liquid.
Confirmation of Sunscreening Effect
Composition prepared in EXAMPLE 23 and cosmetic liquid according to Control
2 were, respectively, applied on the skin and their effect at practical
use in beach was tested. On each of right or left half area of the back of
ten respective male and female, each sample solution was applied, and the
degree of suntan was examined and obtained results was listed in Table 8.
Estimation was performed according to above described estimation criteria.
TABLE 8
______________________________________
Estimation Area applied with
Area applied with
criteria EXAMPLE 24 control 2
______________________________________
.smallcircle.
18 12
.DELTA. 2 6
.DELTA. - .times. 0 2
.times. 0 0
Frequency of No itching 7 cases
skin trouble slight rash 1 case
______________________________________
Example 25
Light Stability Effect for Polymer Materials
Each of 0.05, 0.2 and 0.5 part by weight of sample produced according to
EXAMPLE 23 was formulated with 100 parts by weight of polyethylene powder
or polypropylene powder, mixed well using a mixer, then melted and kneaded
using a extruder having the diameter of 25 mm at cylinder temperature of
200.degree. C., and pelletized. Obtained pellets were compacted into
sheets of 0.25 mm thickness at 210.degree. C. to prepare test strips.
Obtained test strips were punched into dumbbell shapes accommodating to a
tension test. Test strip of control which did not contain light
stabilizing agent was prepared, using the above described same method, and
test strips were examined.
Using the WEL-75XS-HS-BEC model xenon sunshine long-life weatherometer
manufactured by Suga Shiken-Kiki Co. Ltd., these test strips were
light-irradiated with black panel temperature of 80.degree. C., and were
examined for lowering in tensile strength over time.
The tension test and calculation of tension strength was performed
according above described methods.
Obtained results were as listed in Table 9. As apparent from the results
shown in Table 9, the aminomethylene barbituric acid derivatives according
to the present invention show prominent stabilizing effect (that is,
elongated time to deterioration).
TABLE 9
______________________________________
(unit: kgf)
200 400 600 800 1000 1200
Name of risin hrs hrs hrs hrs hrs hrs
______________________________________
Polypropylene: no,
3.15 2.13 0 -- -- --
0.05 (wt%) 3.58 3.07 2.91 -- -- --
0.2 (wt%) 3.72 3.46 3.38 -- -- --
0.5 (wt%) 3.98 3.82 2.64 -- -- --
Polyethylene: no, 2.42 2.29 2.25 2.10 1.90 0
0.05 (wt%) 2.68 2.58 2.50 2.48 2.32 2.22
0.2 (wt%) 2.83 2.70 2.62 2.38 2.42 2.38
0.5 (wt%) 2.88 2.80 2.76 2.70 2.64 2.60
______________________________________
Example 26
Synthesis of
3-[4-(2-ethylhexyloxycarbonyl)phenyl-aminomethylene]chroman-2,4-dione
[compound represented by the general formula (I) of which A is (d),
R.sup.6 =hydrogen atom, n=1 and R=2-ethylhexyl]
After stirring suspension containing 0.20 mol of 4-hydroxy coumarin, 0.50
mol of 4-(2-ethylhexyloxycarbonyl)-N-formanilide and 25 ml of toluene,
0.50 mol of phosphorus oxychloride is added to the suspension over 15
minutes. During the addition, temperature is maintained at 45.degree. C.
or lower. The suspension is further stirred for 10 minutes, then 250 ml of
hot solution of toluene containing 0.48 mol of 4-hydroxy coumarin is added
to at 60 to 65.degree. C., over 45 minutes. The reaction mixture is
constantly stirred and allowed to cool to room temperature, and reaction
is terminated by adding the reaction mixture dropwise into 600 ml of 15%
sodium hydroxide solution. Obtained organic layer is being washed with 200
ml of saturated aqueous solution of sodium chloride. The organic layer is
fractionated, allowed to dry on anhydrous sodium sulfate, filtrated and
concentrated to obtain crude product.
Purified product having the melting point of 179 to 180.degree. C. is
obtained through recrystalization from dioxane.
Ultraviolet absorption spectrum (chloroform): .lambda. max(nm) 375
(.epsilon. max 38,500);
Infrared absorption spectrum: cm.sup.-1 (KBr) 3420 (NH), 1708 (ester and
lactone C.dbd.O), 1642 (4-position C.dbd.O ), 1630 (--NH--CH.dbd.C.dbd.),
1280 (C--O--C).
Example 27
Synthesis of 3-(4-ethoxycarbonylphenylaminomethylene)chroman-2,4-dione
[compound represented by the general formula (I) of which A is (d),
R.sup.6 =hydrogen atom, n=1 and R=ethyl]
Same procedure used in EXAMPLE 26, except that
4-ethoxycarbonyl-N-formanilide was used instead of
4-(2-ethylhexyloxycarbonyl)-N-formanilide, was repeated.
Melting point: 233 to 234.degree. C.;
Ultraviolet absorption spectrum (chloroform): .lambda. max(nm) 374,
(.epsilon. max 38,200);
Infrared absorption spectrum: cm.sup.-1 (KBr) 3430 (NH), 1718 (ester and
lactone C.dbd.O ), 1650 (4-position C.dbd.O ), 1638 (--NH--CH.dbd.C.dbd.),
1278 (C--O--C).
Example 28
Synthesis of 3-(4-n-propoxycarbonylphenylamino methylene)chroman-2,4-dione
[compound represented by the general formula (I) of which A is (d),
R.sup.6 =hydrogen atom, n=1 and R=n-propyl]
Same procedure used in EXAMPLE 26, except that
4-n-propoxycarbonyl-N-formanilide was used instead of
4-(2-ethylhexyloxycarbonyl)-N-formanilide, was repeated.
Melting point: 211.5 to 212.5.degree. C.
Ultraviolet absorption spectrum (chloroform): .lambda. max(nm) 375
(.epsilon. max 37,600);
Infrared absorption spectrum: cm.sup.-1 (KBr) 3430 (NH), 1718 (ester and
lactone C.dbd.O ), 1650 (4-position C.dbd.O ), 1630 (--NH--CH.dbd.C.dbd.),
1278 (C--O--C).
Example 29
Synthesis of 3-(4-isopropoxycarbonylphenylaminomethylene)chroman-2,4-dione
[compound represented by the general formula (I) of which A is (d),
R.sup.6 =hydrogen atom, n=1 and R=isopropyl]
Same procedure used in EXAMPLE 26, except that
4-isopropoxycarbonyl-N-formanilide was used instead of
4-(2-ethylhexyloxycarbonyl)-N-formanilide, was repeated.
Melting point: 206.5 to 207.degree. C.;
Ultraviolet absorption spectrum (chloroform): .lambda. max(nm) 374
(.epsilon. max 35,600);
Infrared absorption spectrum: cm.sup.-1 (KBr) 3430 (NH), 1710 (ester and
lactone C.dbd.O ), 1650 (4-position C.dbd.O ), 1630 (--NH--CH.dbd.C.dbd.),
1278 (C--O--C).
Example 30
Synthesis of 3-(4-n-butoxycarbonylphenylaminomethylene)chroman-2,4-dione
[compound represented by the general formula (I) of which A is (d),
R.sup.6 =hydrogen atom, n=1 and R=n-butyl]
Same procedure used in EXAMPLE 26, except that
4-n-butoxycarbonyl-N-formanilide was used instead of
4-(2-ethylhexyloxycarbonyl)-N-formanilide, was repeated.
Melting point: 207 to 207.5.degree. C.;
Ultraviolet absorption spectrum (chloroform): .lambda. max(nm) 375
(.epsilon. max 38,400);
Infrared absorption spectrum: cm.sup.-1 (KBr) 3430 (NH), 1720 (ester and
lactone C.dbd.O ), 1650 (4-position C.dbd.O ), 1630 (--NH--CH.dbd.C.dbd.),
1275 (C--O--C).
Example 31
Synthesis of 3-(4-isobutoxycarbonylphenylaminomethylene)chroman-2,4-dione
[compound represented by the general formula (I) of which A is (d),
R.sup.6 =hydrogen atom, n=1 and R=isobutyl]
Same procedure used in EXAMPLE 26, except that
4-isobutoxycarbonyl-N-formanilide was used instead of
4-(2-ethylhexyloxycarbonyl)-N-formanilide, was repeated.
Melting point: 221.5 to 222.5.degree. C.;
Ultraviolet absorption spectrum (chloroform): .lambda. max(nm) 376
(.epsilon. max 38,000)
Infrared absorption spectrum: cm.sup.-1 (KBr) 3440 (NH), 1718 (ester and
lactone C.dbd.O ), 1650 (4-position C.dbd.O ), 1628 (--NH--CH.dbd.C.dbd.),
1272 (C--O--C).
Example 32
Practical examples of formulation of skin ointment according to the present
invention hereunder will be described.
According to the formulation listed in Table 10, a cosmetic liquid
containing the compound according to EXAMPLE 26, that is
3-[4-(2-ethylhexyloxycarbonyl)phenylaminomethylene]chroman-2,4-dione and
as control cosmetic liquids, cosmetic liquids containing compound of
Control 1, that is 2,2',4,4'-tetrahydroxybenzophenone, and compound of
Control 2, that is 2-ethylhexyl p-methoxycinnamate, respectively, were
prepared.
TABLE 10
______________________________________
Composition EXAMPLE 32 Control 1
Control 2
______________________________________
ethanol 8.0 8.0 8.0
glycerin 2.0 2.0 2.0
citric acid 0.02 0.02 0.02
sodium citrate 0.1 0.1 0.1
methylparaben 0.05 0.05 0.05
POE hardened caster oil 0.5 0.5 0.5
perfume some some some
compound of EXAMPLE 26 1.0 -- --
compound of Control 1 -- 1.0 --
compound of Control 2 -- -- 1.0
propylene glycol 7.0 7.0 7.0
purified water rest rest rest
______________________________________
Control 1 exhibited pale yellow and was not suitable for cosmetic liquid.
Example 33
Confirmation of Sunscreening Effect
Cosmetic liquid of the present invention, containing the compound produced
according to EXAMPLE 30, in stead of compound produced according to
EXAMPLE 26 which was used in EXAMPLE 32, and cosmetic liquid according to
Control 2 were, respectively, applied on the skin and their effect at
practical use in beach was tested. On each of right or left half area of
the back of ten respective male and female, each sample solution was
applied, and the degree of suntan was examined and obtained results was
listed in Table 11. Estimation was performed according to above described
estimation criteria.
TABLE 11
______________________________________
Estimation Area applied with
Area applied with
criteria EXAMPLE 33 Control 2
______________________________________
.smallcircle.
19 17
.DELTA. 1 2
.DELTA. - .times. 0 1
.times. 0 0
Frequency of No itching 3 cases
skin trouble slight rash 1 case
______________________________________
Example 34
Light Stability Effect for Polymer Materials
Each of 0.05, 0.2 and 0.5 part by weight of sample produced according to
EXAMPLE 26 was formulated with 100 parts by weight of polyethylene powder
or polypropylene powder, mixed well using a mixer, then melted and kneaded
using a extruder having the diameter of 25 mm at cylinder temperature of
200.degree. C., and pelletized. Obtained pellets were compacted into
sheets of 0.25 mm thickness at 210.degree. C., to prepare test strips.
Obtained test strips were punched into dumbbell shapes accommodating to a
tension test. Test strip of control which did not contain light
stabilizing agent was prepared, using the above described same method, and
test strips were examined.
Using the WEL-75XS-HS-BEC model xenon sunshine long-life weatherometer
manufactured by Suga Shiken-Kiki Co. Ltd., these test strips were
light-irradiated with black panel temperature of 80.degree. C., and were
examined for lowering in tensile strength over time.
The tension test and calculation of tension strength was performed
according above described methods.
Obtained results were as listed in Table 12. As apparent from the results
shown in Table 12, the aminomethylene chroman derivatives according to the
present invention show prominent stabilizing effect (that is, elongated
time to deterioration).
TABLE 12
______________________________________
(unit: kgf)
200 400 600 800 1000 1200
Name of resin hrs hrs hrs hrs hrs hrs
______________________________________
Polypropylene: no,
3.15 2.13 0 -- -- --
0.05 (wt%) 3.56 3.04 2.90 -- -- --
0.2 (wt%) 3.70 3.40 3.36 -- -- --
0.5 (wt%) 3.92 3.81 3.60 -- -- --
Polyethylene: no, 2.42 2.26 2.25 2.10 1.90 0
0.05 (wt%) 2.82 2.72 2.60 2.63 2.50 2.40
0.2 (wt%) 2.80 2.92 2.80 2.74 258 2.60
0.5 (wt%) 3.02 3.02 2.92 2.80 2.70 2.80
______________________________________
Example 35
Synthesis of
2,2-dimethyl-5-[4-(2-ethylhexyloxycarbonyl)phenylaminomethylene]-1,3-dioxa
ne-4,6-dione [compound represented by the general formula (I) of which A is
(e), R.sup.7 =R.sup.8 =methyl and R=2-ethylhexyl]
After stirring suspension containing 0.20 mol of Meldrum's acid, 0.50 mol
of 4-(2-ethylhexyloxycarbonyl)-N-formanilide and 25 ml of toluene, 0.50
mol of phosphorus oxychloride is added to the suspension over 15 minutes.
During the addition, temperature is maintained at 45.degree. C. or lower.
The suspension is further stirred for 10 minutes, then 250 ml of hot
solution of toluene containing 0.30 mol of Meldrum's acid is added to at
60 to 65.degree. C., over 45 minutes. The reaction mixture is constantly
stirred and allowed to cool to room temperature, and reaction is
terminated by adding the reaction mixture dropwise into 600 ml of 15%
sodium hydroxide solution. Obtained organic layer is being washed with 200
ml of saturated aqueous solution of sodium chloride. The organic layer is
fractionated, allowed to dry on anhydrous sodium sulfate, filtrated and
concentrated to obtain crude product.
Purified product having the melting point of 148.5 to 149.5.degree. C. is
obtained through recrystalization from dioxane.
Ultraviolet absorption spectrum (chloroform): .lambda. max(nm) 339,
.epsilon. max 35,500;
Infrared absorption spectrum (chloroform): cm.sup.-1 (KBr) 3420(NH), 1708
(ester and lactone C.dbd.O ), 1642 (4-position C.dbd.O ), 1630
(--NH--CH.dbd.C.dbd.), 1280 (C--O--C).
Example 36
Synthesis of
2,2-dimethyl-5-(4-ethoxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-dion
e [compound represented by the general formula (I) of which A is (e),
R.sup.7 =R.sup.8 =methyl and R=ethyl]
Same procedure used in EXAMPLE 35, except that
4-ethoxycarbonyl-N-formanilide was used instead of
4-(2-ethylhexyloxycarbonyl)-N-formanilide, was repeated.
Melting point: 184 to 184.5.degree. C.;
Ultraviolet absorption spectrum (chloroform): .lambda. max (nm) 338,
.epsilon. max 35,700;
Infrared absorption spectrum: cm.sup.-1 (KBr) 3220 (NH), 1730 (lactone
C.dbd.O ), 1718 (ester C.dbd.O ), 1688 (4-position C.dbd.O ), 1652
(--NH--CH.dbd.C.dbd.).
Example 37
Synthesis of
2,2-dimethyl-5-(4-n-propoxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-d
ione [compound represented by the general formula (I) of which A is (e),
R.sup.7 =R.sup.8 =methyl and R=n-propyl]
Same procedure used in EXAMPLE 35, except that
4-(n-proxycarbonyl)-N-formanilide was used instead of
4-(2-ethylhexyloxycarbonyl)-N-formanilide, was repeated.
Melting point: 154 to 155.degree. C.;
Ultraviolet absorption spectrum (chloroform): .lambda. max (nm) 337,
.epsilon. max max 35,900;
Infrared absorption spectrum: cm.sup.-1 (KBr) 3229 (NH), 1732 (lactone
C.dbd.O ), 1718 (ester C.dbd.O ), 1682 (4-position C.dbd.O ), 1638
(--NH--CH.dbd.C.dbd.).
Example 38
Synthesis of
2,2-dimethyl-5-(4-isopropoxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-
dione [compound represented by the general formula (I) of which A is (e),
R.sup.7 =R.sup.8 =isopropyl and R=isopropyl]
Same procedure used in EXAMPLE 35, except that
4-(isoproxycarbonyl)-N-formanilide was used instead of
4-(2-ethylhexyloxycarbonyl)-N-formanilide, was repeated.
Melting point: 185 to 186.degree. C.;
Ultraviolet absorption spectrum (chloroform): .lambda. max(nm) 338,
.epsilon. max 35,200;
Infrared absorption spectrum: cm.sup.-1 (KBr) 3220 (NH), 1736 (lactone
C.dbd.O ), 1718 (ester C.dbd.O ), 1682 (4-position C.dbd.O ), 1640
(--NH--CH.dbd.C.dbd.).
Example 39
Synthesis of
2,2-dimethyl-5-(4-n-butoxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-di
one [compound represented by the general formula (I) of which A is (e),
R.sup.7 =R.sup.8 =methyl and R=n-butyl]
Same procedure used in EXAMPLE 35, except that
4-(n-butoxycarbonyl)-N-formanilide was used instead of
4-(2-ethylhexyloxycarbonyl)-N-formanilide, was repeated.
Melting point: 161 to 162.degree. C.;
Ultraviolet absorption spectrum (chloroform): .lambda. max(nm) 338,
.epsilon. max 35,200;
Infrared absorption spectrum: cm.sup.-1 (KBr) 3220 (NH), 1738 (lactone
C.dbd.O ), 1716 (ester C.dbd.O ), 1680 (4-position C.dbd.O ), 1630
(--NH--CH.dbd.C.dbd.).
Example 40
Synthesis of
2,2-dimethyl-5-(4-isobutoxycarbonylphenylaminomethylene)-1,3-dioxane-4,6-d
ione [compound represented by the general formula (I) of which A is (e),
R.sup.7 =R.sup.8 =methyl and R=isobutyl]
Same procedure used in EXAMPLE 35, except that
4-(isobutoxycarbonyl)-N-formanilide was used instead of
4-(2-ethylhexyloxycarbonyl)-N-formanilide, was repeated.
Melting point: 186.5 to 187.5.degree. C.;
Ultraviolet absorption spectrum (chloroform): .lambda. max(nm) 338,
.epsilon. max 43,400;
Infrared absorption spectrum: cm.sup.-1 (KBr) 3220 (NH), 1732 (lactone
C.dbd.O ), 1705 (ester C.dbd.O ), 1680 (4-position C.dbd.O ), 1632
(--NH--CH.dbd.C.dbd.).
Example 41
Practical examples of formulation of skin ointment according to the present
invention hereunder will be described.
According to the formulation listed in Table 13, a cosmetic liquid
containing the compound according to EXAMPLE 35, that is
2,2-dimethyl-5-[4-(2-ethylhexyloxycarbonyl)phenylaminomethylene]-1,3-dioxa
ne-4,6-dione and as control cosmetic liquids, cosmetic liquids containing
compound of Control 1, that is 2,2',4,4'-tetrahydroxybenzophenone, and
compound of Control 2, that is 2-ethylhexyl p-methoxycinnamate,
respectively, were prepared.
TABLE 13
______________________________________
Composition EXAMPLE 41 Control 1
Control 2
______________________________________
ethanol 8.0 8.0 8.0
glycerin 2.0 2.0 2.0
citric acid 0.02 0.02 0.02
sodium citrate 0.1 0.1 0.1
methylparaben 0.05 0.05 0.05
POE hardened caster oil 0.5 0.5 0.5
perfume some some some
compound of EXAMPLE 35 1.0 -- --
compound of Control 1 -- 1.0 --
compound of Control 2 -- -- 1.0
propylene glycol 7.0 7.0 7.0
purified water rest rest rest
______________________________________
Control 1 exhibited pale yellow and was not suitable for cosmetic liquid.
Example 42
Confirmation of Sunscreening Effect
Cosmetic liquid of the present invention, containing the compound produced
according to EXAMPLE 39, in stead of compound produced according to
EXAMPLE 35 which was used in EXAMPLE 41, and cosmetic liquid according to
Control 2 were, respectively, applied on the skin and their effect at
practical use in beach was tested. On each of right or left half area of
the back of ten respective male and female, each sample solution was
applied, and the degree of suntan was examined and obtained results was
listed in Table 14. Estimation was performed according to above described
estimation criteria.
TABLE 14
______________________________________
Estimation Area applied with
Area applied with
criteria EXAMPLE 41 Control 2
______________________________________
.smallcircle.
18 17
.DELTA. 1 2
.DELTA. - .times. 1 1
.times. 0 0
Frequency of itching 1 case itching 3 cases
skin trouble slight rash 1 case
______________________________________
Example 43
Light Stability Effect for Polymer Materials
Each of 0.05, 0.2 and 0.5 part by weight of sample produced according to
EXAMPLE 35 was formulated with 100 parts by weight of polyethylene powder
or polypropylene powder, mixed well using a mixer, then melted and kneaded
using a extruder having the diameter of 25 mm at cylinder temperature of
200.degree. C., and pelletized. Obtained pellets were compacted into
sheets of 0.25 mm thickness at 210.degree. C. to prepare test strips.
Obtained test strips were punched into dumbbell shapes accommodating to a
tension test. Test strip of control which did not contain light
stabilizing agent was prepared, using the above described same method, and
test strips were examined.
Using the WEL-75XS-HS-BEC model xenon sunshine long-life weatherometer
manufactured by Suga Shiken-Kiki Co.Ltd., these test strips were
light-irradiated with black panel temperature of 80.degree. C., and were
examined for lowering in tensile strength over time.
The tension test and calculation of tension strength was performed
according above described methods.
Obtained results were as listed in Table 15. As apparent from the results
shown in Table 15, the aminomethylene chroman derivatives according to the
present invention show prominent stabilizing effect (that is, elongated
time to deterioration).
TABLE 15
______________________________________
(unit: kgf)
200 400 600 800 1000 1200
Name of resin hrs hrs hrs hrs hrs hrs
______________________________________
Polypropylene: no,
3.15 2.13 0 -- -- --
0.05 (wt%) 3.68 3.17 3.01 -- -- --
0.2 (wt%) 3.76 3.44 3.36 -- -- --
0.5 (wt%) 3.96 3.80 3.62 -- -- --
Polyethylene: no, 2.42 2.29 2.25 2.10 1.90 0
0.05 (wt%) 2.86 2.76 2.68 2.66 2.50 2.21
0.2 (wt%) 2.81 2.88 2.80 2.76 2.60 2.39
0.5 (wt%) 3.06 2.98 2.94 2.88 2,82 2.78
______________________________________
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